Half-metallocene compounds and catalyst compositions

ABSTRACT

The present invention provides polymerization catalyst compositions employing half-metallocene compounds with a heteroatom-containing ligand bound to the transition metal. Methods for making these hybrid metallocene compounds and for using such compounds in catalyst compositions for the polymerization of olefins also are provided.

BACKGROUND OF THE INVENTION

The present invention relates generally to the field of olefinpolymerization catalysis, catalyst compositions, methods for thepolymerization of olefins, and polyolefins. More specifically, thisinvention relates to half-metallocene compounds with aheteroatom-containing ligand bound to the transition metal, and catalystcompositions employing such hybrid compounds.

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.One method that can be used to produce such polyolefins employs achromium-based catalyst system. HDPE and LLDPE resins produced using achromium-based catalyst system generally have a broad molecular weightdistribution. For instance, resins having a polydispersity index (PDI,or Mw/Mn) greater than 6 are not unusual. Polyolefin resins producedusing a chromium catalyst also can have a low level of long chainbranching. This combination of properties is difficult to duplicate withother commercially viable catalyst systems. Metallocene catalysts, forexample, generally can produce polyolefins with a much narrowermolecular weight distribution and either have too little, or too much,long chain branching. Likewise, Ziegler-type catalyst systems canproduce polyolefin resins which are typically much narrower in molecularweight distribution and have substantially no long chain branching.Polyolefin resins produced using a Ballard type catalyst generally canbe too high in molecular weight, too broad in molecular weightdistribution, and contain too much long chain branching.

It would be beneficial to have a non-chromium catalyst system that couldproduce an olefin polymer having the desired combination of a relativelybroad molecular weight distribution and a relatively low level of longchain branching. Accordingly, it is to this end that the presentinvention is directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to new catalyst compositions,methods for preparing catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In particular, the present invention relates tohalf-metallocene compounds with a heteroatom-containing ligand bound tothe transition metal, and catalyst compositions employing such hybridmetallocene compounds. Catalyst compositions of the present inventionwhich contain these hybrid metallocene compounds can be used to produce,for example, ethylene-based homopolymers and copolymers.

Disclosed and described herein are novel hybrid metallocene compoundshaving a metallocene moiety and a heteroatom-containing ligand.According to one aspect of the present invention, these unbridged hybridmetallocene compounds can have the formula:

In formula (I), M can be Zr, Hf, or Ti; X¹ and X² independently can be ahalide or a substituted or unsubstituted aliphatic, aromatic, or cyclicgroup, or a combination thereof; X³ can be a substituted orunsubstituted cyclopentadienyl, indenyl, or fluorenyl group, wherein anysubstituents on X³ independently are a hydrogen atom or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof; and X⁴ can be —O—R^(A), —NH—R^(A), —PH—R^(A), —S—R^(A),—O—Si—R^(B) ₃, or —O—C—R^(B) ₃. R^(A) can be an aryl group substitutedwith a first alkoxy group and a second substituent selected from analkyl, cycloalkyl, or second alkoxy group, wherein any additionalsubstituents on R^(A) independently are a hydrogen atom or an alkyl,cycloalkyl, or alkoxy group. Each R^(B) independently can be a hydrogenatom or a substituted or unsubstituted aliphatic, aromatic, or cyclicgroup, or a combination thereof.

Catalyst compositions containing these unbridged hybrid metallocenecompounds are also provided by the present invention. In one aspect, acatalyst composition is disclosed which comprises a hybrid metallocenecompound and an activator. This catalyst composition can furthercomprise an organoaluminum compound. In some aspects, the activator cancomprise an activator-support, while in other aspects, the activator cancomprise an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, or combinations thereof.

In accordance with certain aspects of the invention, novel hybridmetallocene compounds and catalyst compositions comprising these hybridmetallocene compounds and an activator are disclosed and described. Forinstance, these hybrid metallocene compounds can have one of thefollowing formulas:

In formula (III) and formula (IV), each M independently can be Zr, Hf,or Ti; each X¹ and X² independently can be a halide or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof; and each X³ independently can be a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, wherein any substituentson X³ independently are a hydrogen atom or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof.

Catalyst compositions containing a hybrid metallocene compound havingformula (III) or formula (IV) can further comprise an organoaluminumcompound, and the activator can comprise an activator-support, analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, or combinations thereof.

The present invention also contemplates olefin polymerization processes.Such processes can comprise contacting a catalyst composition with anolefin monomer and optionally an olefin comonomer under polymerizationconditions to produce an olefin polymer. Generally, the catalystcomposition employed can comprise any of the hybrid metallocenecompounds disclosed herein and any of the activators disclosed herein.Further, organoaluminum compounds also can be utilized in thepolymerization processes.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, terpolymers, etc., can be used to producevarious articles of manufacture.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents the structures and abbreviations for certain hybridmetallocene or half-metallocene compounds discussed herein.

FIG. 2 presents a ¹H-NMR plot of the MET-H product of Example 2.

FIG. 3 presents a ¹H-NMR plot of the MET-J product of Example 4.

FIG. 4 presents a ¹H-NMR plot of the MET-K product of Example 5.

FIG. 5 presents a plot of the molecular weight distributions of thepolymer of Example 14 and of a comparative polymer produced using astandard metallocene catalyst system.

FIG. 6 presents a plot of the molecular weight distributions of thepolymers of Examples 20 and 22.

FIG. 7 presents a plot of the molecular weight distribution of thepolymer of Example 47.

FIG. 8 presents a plot of the radius of gyration versus the logarithm ofmolecular weight for a linear standard and the polymers of Examples 34and 56.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. To the extent that any definition or usage provided by anydocument incorporated herein by reference conflicts with the definitionor usage provided herein, the definition or usage provided hereincontrols.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer would be categorized an as ethylene/1-hexenecopolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process would involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “co-catalyst” is used generally herein to refer toorganoaluminum compounds that can constitute one component of a catalystcomposition. Additionally, “co-catalyst” can refer to other componentsof a catalyst composition including, but not limited to, aluminoxanes,organoboron or organoborate compounds, and ionizing ionic compounds, asdisclosed herein, when used in addition to an activator-support. Theterm “co-catalyst” is used regardless of the actual function of thecompound or any chemical mechanism by which the compound may operate. Inone aspect of this invention, the term “co-catalyst” can be used todistinguish that component of the catalyst composition from the hybridmetallocene compound(s).

The terms “chemically-treated solid oxide,” “activator-support,”“treated solid oxide compound,” and the like, are used herein toindicate a solid, inorganic oxide of relatively high porosity, which canexhibit Lewis acidic or Brønsted acidic behavior, and which has beentreated with an electron-withdrawing component, typically an anion, andwhich is calcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide can comprise a calcined contact product of at least onesolid oxide with at least one electron-withdrawing anion sourcecompound. Typically, the chemically-treated solid oxide comprises atleast one acidic solid oxide compound. The terms “support” and“activator-support” are not used to imply these components are inert,and such components should not be construed as an inert component of thecatalyst composition. The activator-support of the present invention canbe a chemically-treated solid oxide. The term “activator,” as usedherein, refers generally to a substance that is capable of converting ametallocene component into a catalyst that can polymerize olefins, orconverting a contact product of a metallocene component and a componentthat provides an activatable ligand (e.g., an alkyl, a hydride) to themetallocene, when the metallocene compound does not already comprisesuch a ligand, into a catalyst that can polymerize olefins. This term isused regardless of the actual activating mechanism. Illustrativeactivators include activator-supports, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.Aluminoxanes, organoboron or organoborate compounds, and ionizing ioniccompounds generally are referred to as activators if used in a catalystcomposition in which an activator-support is not present. If thecatalyst composition contains an activator-support, then thealuminoxane, organoboron or organoborate, and ionizing ionic materialsare typically referred to as co-catalysts.

The term “fluoroorgano boron compound” is used herein with its ordinarymeaning to refer to neutral compounds of the form BY₃. The term“fluoroorgano borate compound” also has its usual meaning to refer tothe monoanionic salts of a fluoroorgano boron compound of the form[cation]⁺[BY₄]⁻, where Y represents a fluorinated organic group.Materials of these types are generally and collectively referred to as“organoboron or organoborate compounds.”

The term “hybrid metallocene,” as used herein, describes an unbridgedhalf-metallocene compound with a heteroatom-containing ligand bound tothe transition metal. The hybrid metallocenes of this invention containone η³ to η⁵-cyclopentadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands include hydrogen, therefore thedescription “substituted derivatives thereof” in this inventioncomprises partially saturated ligands such as tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl,partially saturated fluorenyl, substituted partially saturated indenyl,substituted partially saturated fluorenyl, and the like. In somecontexts, the hybrid metallocene may be referred to simply as the“catalyst,” in much the same way the term “co-catalyst” may be usedherein to refer to, for example, an organoaluminum compound.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of theclaimed catalyst composition/mixture/system, the nature of the activecatalytic site, or the fate of the co-catalyst, the metallocenecompound(s), any olefin monomer used to prepare a precontacted mixture,or the activator (e.g., activator-support), after combining thesecomponents. Therefore, the terms “catalyst composition,” “catalystmixture,” “catalyst system,” and the like, encompass the initialstarting components of the composition, as well as whatever products)may result from contacting these initial starting components, and thisis inclusive of both heterogeneous and homogenous catalyst systems orcompositions.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another. Similarly, the term“contacting” is used herein to refer to materials which may be blended,mixed, slurried, dissolved, reacted, treated, or otherwise contacted insome other manner.

The term “precontacted” mixture is used herein to describe a firstmixture of catalyst components that are contacted for a first period oftime prior to the first mixture being used to form a “postcontacted” orsecond mixture of catalyst components that are contacted for a secondperiod of time. Typically, the precontacted mixture can describe amixture of metallocene compound (one or more than one), olefin monomer(or monomers), and organoaluminum compound (or compounds), before thismixture is contacted with an activator-support(s) and optionaladditional organoaluminum compound. Thus, precontacted describescomponents that are used to contact each other, but prior to contactingthe components in the second, postcontacted mixture. Accordingly, thisinvention may occasionally distinguish between a component used toprepare the precontacted mixture and that component after the mixturehas been prepared. For example, according to this description, it ispossible for the precontacted organoaluminum compound, once it iscontacted with the metallocene compound and the olefin monomer, to havereacted to form at least one different chemical compound, formulation,or structure from the distinct organoaluminum compound used to preparethe precontacted mixture. In this case, the precontacted organoaluminumcompound or component is described as comprising an organoaluminumcompound that was used to prepare the precontacted mixture.

Additionally, the precontacted mixture can describe a mixture ofmetallocene compound(s) and organoaluminum compound(s), prior tocontacting this mixture with an activator-support(s). This precontactedmixture also can describe a mixture of metallocene compound(s), olefinmonomer(s), and activator-support(s), before this mixture is contactedwith an organoaluminum co-catalyst compound or compounds.

Similarly, the term “postcontacted” mixture is used herein to describe asecond mixture of catalyst components that are contacted for a secondperiod of time, and one constituent of which is the “precontacted” orfirst mixture of catalyst components that were contacted for a firstperiod of time. Typically, the term “postcontacted” mixture is usedherein to describe the mixture of metallocene compound(s), olefinmonomer(s), organoaluminum compound(s), and activator-support(s) formedfrom contacting the precontacted mixture of a portion of thesecomponents with any additional components added to make up thepostcontacted mixture. Often, the activator-support can comprise achemically-treated solid oxide. For instance, the additional componentadded to make up the postcontacted mixture can be a chemically-treatedsolid oxide (one or more than one), and optionally, can include anorganoaluminum compound which is the same as or different from theorganoaluminum compound used to prepare the precontacted mixture, asdescribed herein. Accordingly, this invention may also occasionallydistinguish between a component used to prepare the postcontactedmixture and that component after the mixture has been prepared.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

For any particular compound disclosed herein, any general or specificstructure presented also encompasses all conformational isomers,regioisomers, and stereoisomers that may arise from a particular set ofsubstituents, unless stated otherwise. Similarly, unless statedotherwise, the general or specific structure also encompasses allenantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, aswould be recognized by a skilled artisan.

The term “hydrocarbyl” is used herein to specify a hydrocarbon radicalgroup that includes, but is not limited to, aryl, alkyl, cycloalkyl,alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl,aralkynyl, and the like, and includes all substituted, unsubstituted,branched, linear, heteroatom substituted derivatives thereof.

Applicants disclose several types of ranges in the present invention.These include, but are not limited to, a range of number of atoms, arange of integers, a range of weight ratios, a range of molar ratios, arange of molecular weights, a range of temperatures, and so forth. WhenApplicants disclose or claim a range of any type, Applicants' intent isto disclose or claim individually each possible number that such a rangecould reasonably encompass, including end points of the range as well asany sub-ranges and combinations of sub-ranges encompassed therein. Forexample, when the Applicants disclose or claim a chemical moiety havinga certain number of carbon atoms, Applicants' intent is to disclose orclaim individually every possible number that such a range couldencompass, consistent with the disclosure herein. For example, thedisclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group, or inalternative language a hydrocarbyl group having up to 18 carbon atoms,as used herein, refers to a moiety that can be selected independentlyfrom a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, or 18 carbon atoms, as well as any range betweenthese two numbers (for example, a C₁ to C₈ hydrocarbyl group), and alsoincluding any combination of ranges between these two numbers (forexample, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbyl group).

Similarly, another representative example follows for the ratio of Mw/Mnprovided in one aspect of this invention. By a disclosure that the ratioof Mw/Mn can be in a range from about 3 to about 20, Applicants intendto recite that Mw/Mn can be about 3, about 4, about 5, about 6, about 7,about 8, about 9, about 10, about 11, about 12, about 13, about 14,about 15, about 16, about 17, about 18, about 19, or about 20.Additionally, the Mw/Mn ratio can be within any range from about 3 toabout 20 (for example, from about 5 to about 15), and this also includesany combination of ranges between about 3 and about 20 (for example,Mw/Mn can be in a range from about 4 to about 6, or from about 8 toabout 13). Likewise, all other ranges disclosed herein should beinterpreted in a manner similar to these two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a hybridmetallocene compound” is meant to encompass one, or mixtures orcombinations of more than one, activator-support or hybrid metallocenecompound, respectively.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps. For example, a catalyst composition of the present invention cancomprise; alternatively, can consist essentially of; or alternatively,can consist of; (i) a hybrid metallocene compound and (ii) an activator.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing catalyst compositions, methods forusing the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto half-metallocene compounds with a heteroatom-containing ligand boundto the transition metal, and catalyst compositions employing such hybridmetallocene compounds.

Hybrid Metallocene Compounds

The present invention discloses novel hybrid metallocene compoundshaving a metallocene moiety and a heteroatom-containing ligand, andmethods of making these compounds. For convenience, these compounds willbe referred to herein as hybrid metallocene compounds. In one aspect ofthis invention, the unbridged hybrid metallocene compound can have theformula:

wherein:

M can be Zr, Hf, or Ti;

X¹ and X² independently can be a halide or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof;

X³ can be a substituted or unsubstituted cyclopentadienyl, indenyl, orfluorenyl group, wherein any substituents on X³ independently can be ahydrogen atom or a substituted or unsubstituted aliphatic, aromatic, orcyclic group, or a combination thereof;

-   -   X⁴ can be —O—R^(A), —NH—R^(A), —PH—R^(A), —S—R^(A), —O—Si—R^(B)        ₃, or —O—C—R^(B) ₃; wherein:        -   R^(A) can be an aryl group substituted with a first alkoxy            group and a second substituent selected from an alkyl,            cycloalkyl, or second alkoxy group, wherein any additional            substituents on R^(A) independently can be a hydrogen atom            or an alkyl, cycloalkyl, or alkoxy group; and        -   each R^(B) independently can be a hydrogen atom or a            substituted or unsubstituted aliphatic, aromatic, or cyclic            group, or a combination thereof.

Unless otherwise specified, formula (I) above, any other structuralformulas disclosed herein, and any hybrid metallocene species orcompound disclosed herein are not designed to show stereochemistry orisomeric positioning of the different moieties (e.g., these formulas arenot intended to display cis or trans isomers, or R or Sdiastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures.

The metal in formula (I), M, can be Zr, Hf, or Ti. In one aspect of thepresent invention, M can be either Zr or Ti, while in another aspect, Mcan be Ti.

In formula (I), X¹ and X² independently can be a halide, such as afluorine, chlorine, bromine, or iodine atom. As used herein, analiphatic group includes linear or branched alkyl and alkenyl groups.Generally, the aliphatic group can contain from 1 to 20 carbon atoms.Unless otherwise specified, alkyl and alkenyl groups described hereinare intended to include all structural isomers, linear or branched, of agiven moiety; for example, all enantiomers and all diastereomers areincluded within this definition. As an example, unless otherwisespecified, the term propyl is meant to include n-propyl and iso-propyl,while the term butyl is meant to include n-butyl, iso-butyl, t-butyl,sec-butyl, and so forth. For instance, non-limiting examples of octylisomers can include 2-ethyl hexyl and neooctyl. Examples of suitablealkyl groups which can be employed in the present invention can include,but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, or decyl, and the like. Examples of alkenyl groupswithin the scope of the present invention can include, but are notlimited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,octenyl, nonenyl, decenyl, and the like.

Aromatic groups and combinations with aliphatic groups include aryl andarylalkyl groups, and these can include, but are not limited to, phenyl,alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl,phenyl-substituted alkyl, naphthyl-substituted alkyl, and the like.Generally, such groups and combinations of groups can contain less than20 carbon atoms. Hence, non-limiting examples of such moieties that canbe used in the present invention can include phenyl, tolyl, benzyl,dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl,propyl-2-phenylethyl, and the like. Cyclic groups can include cycloalkyland cycloalkenyl moieties and such moieties can include, but are notlimited to, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, andthe like. One example of a combination including a cyclic group is acyclohexylphenyl group. Unless otherwise specified, any substitutedaromatic or cyclic moiety used herein is meant to include allregioisomers; for example, the term tolyl is meant to include anypossible substituent position, that is, ortho, meta, or para.

In one aspect of the present invention, X¹ and X² independently can be asubstituted or unsubstituted aliphatic group having from 1 to 20 carbonatoms. In another aspect, X¹ and X² independently can be methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. In stillanother aspect, either X¹ or X², or both, can be trimethylsilylmethyl.In yet another aspect, X¹ and X² independently can be ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. X¹and X² independently can be a substituted or unsubstituted aromaticgroup, for example, having up to 20 carbon atoms, in another aspect ofthe present invention.

In a different aspect, X¹ and X² both can be chlorine atoms. X¹ and X²independently can be phenyl, naphthyl, tolyl, benzyl, dimethylphenyl,trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl,propyl-2-phenylethyl, cyclopentyl, cyclopentenyl, cyclohexyl,cyclohexenyl, or cyclohexylphenyl in other aspects of this invention.Yet, in another aspect, X¹ and X² independently can be methyl, phenyl,benzyl, or a halide. Further, X¹ and X² independently can be methyl,phenyl, benzyl, or a chlorine atom in another aspect of the presentinvention.

In formula (I), X³ can be a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group. In one aspect of thepresent invention, X³ can be a substituted or unsubstitutedcyclopentadienyl group. In another aspect, X³ can be a substituted orunsubstituted indenyl group.

X³ can be an unsubstituted cyclopentadienyl, indenyl, or fluorenylgroup. Alternatively, X³ can have one or more substituents. Anysubstituents on X³ independently can be a hydrogen atom or a substitutedor unsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof. Hydrogen is included, therefore the notion of a substitutedindenyl and substituted fluorenyl can include partially saturatedindenyls and fluorenyls including, but not limited to,tetrahydroindenyls, tetrahydrofluorenyls, and octahydrofluorenyls.Exemplary aliphatics which can be employed in the present invention caninclude alkyls and alkenyls, examples of which can include, but are notlimited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,octenyl, nonenyl, or decenyl, and the like. Illustrate aromatic groupsand combinations with aliphatic groups, as discussed above, can includephenyl, tolyl, benzyl, and the like. Cyclic substituents are alsocontemplated herein, and non-limiting examples were also provided above,including moieties such as cyclopentyl and cyclohexyl.

In one aspect of this invention, each substituent on X³ independentlycan be a hydrogen atom, or a methyl, ethyl, propyl, n-butyl, t-butyl, orhexyl group. In another aspect, substituents on X³ independently can beethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, or a hydrogen atom.

X⁴ in formula (I) can be —O—R^(A), —NH—R^(A), —PH—R^(A), —S—R^(A),—O—Si—R^(B) ₃, or —O—C—R^(B) ₃. In accordance with one aspect of thepresent invention, X⁴ can be —O—R^(A). In accordance with anotheraspect, X⁴ can be —NH—R^(A). In accordance with yet another aspect, X⁴can be —PH—R^(A) or, alternatively, —S—R^(A). In the —O—R^(A),—NH—R^(A), —PH—R^(A), and —S—R^(A) moieties, R^(A) can be an aryl groupsubstituted with a first alkoxy group and a second substituent selectedfrom an alkyl, cycloalkyl, or second alkoxy group. R^(A) can be an arylgroup substituted with a first alkoxy group, and the first alkoxy groupcan have from 1 to 20 carbons atoms, from 1 to 12 carbon atoms, or from1 to 8 carbon atoms. Representative alkoxy groups can include, but arenot limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, andthe like. Thus, the first alkoxy group on R^(A) can be a methoxy group,an ethoxy group, a propoxy group, or a butoxy group, for example.

R^(A) can be substituted with a second substituent selected from analkyl, cycloalkyl, or second alkoxy group. The alkyl group, cycloalkylgroup, and second alkoxy group can be any alkyl group, cycloalkyl group,and alkoxy group disclosed herein. In one aspect, the second substituenton R^(A) can be a methyl group, an ethyl group, a propyl group, an-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group,a methoxy group, an ethoxy group, a propoxy group, or a butoxy group;alternatively, a methyl group, an ethyl group, a propyl group, a n-butylgroup, or a t-butyl group; alternatively, a cyclopentyl group or acyclohexyl group; or alternatively, a methoxy group, an ethoxy group, apropoxy group, or a butoxy group.

In an aspect of this invention, R^(A) can be a disubstituted aryl group,and in a further aspect, R^(A) can be a 2,6-disubstituted aryl group. Inother aspects, R^(A) can be further substituted with additionalsubstituents; generally, such additional substituents independently canbe a hydrogen atom or an alkyl, cycloalkyl, or alkoxy group.

In certain aspects, X⁴ can be —O—R^(A). Non-limiting examples of X⁴ inthese aspects of the invention can include, but are not limited to, thefollowing moieties:

and the like.

In accordance with other aspects of the invention, X⁴ in formula (I) canbe —O—Si—R^(B) ₃ or —O—C—R^(B) ₃; alternatively, X⁴ can be —O—Si—R^(B)₃; or alternatively, X⁴ can be —O—C—R^(B) ₃. Each R^(B) independentlycan be a hydrogen atom or a substituted or unsubstituted aliphatic,aromatic, or cyclic group, or a combination thereof. Each R^(B),therefore, can be the same or different. Exemplary aliphatic, aromatic,or cyclic groups, or combinations thereof, which can be employed asR^(B), independently, can include, but are not limited to, methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, benzyl, tolyl, xylyl, methyl benzyl,1-ethenyl-2-phenyl, 1-ethynyl-2-phenyl, cyclopentyl, cyclohexyl, and thelike.

In an aspect, X⁴ in formula (I) can be —O—Si—R^(B) ₃ or —O—C—R^(B) ₃,and each R^(B) independently can be a hydrogen atom, a methyl group, anethyl group, a propyl group, a n-butyl group, a t-butyl group, a phenylgroup, a benzyl group, a tolyl group, a xylyl group, a methyl benzylgroup, a 1-ethenyl-2-phenyl group, or a 1-ethynyl-2-phenyl group. Inanother aspect, each R^(B) independently can be a methyl group, an ethylgroup, a propyl group, a n-butyl group, a t-butyl group, a phenyl group,a benzyl group, a tolyl group, a xylyl group, a methyl benzyl group, a1-ethenyl-2-phenyl group, or a 1-ethynyl-2-phenyl group. Yet, in anotheraspect, each R^(B) independently can be a phenyl group, a benzyl group,a tolyl group, a xylyl group, a methyl benzyl group, a1-ethenyl-2-phenyl group, or a 1-ethynyl-2-phenyl group. Additionally,X⁴ in formula (I) can be —O—Si—R^(B) ₃ or —O—C—R^(B) ₃, and each R^(B)independently can be a phenyl group, a benzyl group, a methyl benzylgroup, a 1-ethenyl-2-phenyl group, or a 1-ethynyl-2-phenyl group, in aparticular aspect of this invention.

In formula (I), substituted aliphatic, aromatic, or cyclic groups, andcombinations thereof, are disclosed. Such groups described herein areintended to include substituted analogs with substitutions at anyposition on these groups that conform to the normal rules of chemicalvalence. Thus, groups substituted with one or more than one substituentare contemplated.

Such substituents, when present, can be independently selected from anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, a germanium group, a tingroup, a lead group, a boron group, an aluminum group, an inorganicgroup, an organometallic group, or a substituted derivative thereof, anyof which having from 1 to about 20 carbon atoms; a halide; or hydrogen;as long as these groups do not terminate the activity of the catalystcomposition. Examples of each of these substituent groups can include,but are not limited to, the following groups.

Examples of halide substituents, in each occurrence, can includefluoride, chloride, bromide, and iodide.

In each occurrence, oxygen groups are oxygen-containing groups, examplesof which can include, but are not limited to, alkoxy or aryloxy groups(—OR^(X)), —OSiR^(X) ₃, —OPR^(X) ₂, —OAlR^(X) ₂, and the like, includingsubstituted derivatives thereof, wherein R^(X) in each occurrence can bealkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl,or substituted aralkyl having from 1 to 20 carbon atoms. Examples ofalkoxy or aryloxy groups (—OR^(X)) groups can include, but are notlimited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substitutedphenoxy, and the like.

In each occurrence, sulfur groups are sulfur-containing groups, examplesof which can include, but are not limited to, —SR^(X) and the like,including substituted derivatives thereof, wherein R^(X) in eachoccurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl having from 1 to 20 carbonatoms.

In each occurrence, nitrogen groups are nitrogen-containing groups,which can include, but are not limited to, —NR^(X) ₂ and the like,including substituted derivatives thereof, wherein R^(X) in eachoccurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl having from 1 to 20 carbonatoms.

In each occurrence, phosphorus groups are phosphorus-containing groups,which can include, but are not limited to, —PR^(X) ₂, —P(OR^(X))₂, andthe like, including substituted derivatives thereof, wherein R^(X) ineach occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substitutedalkyl, substituted aryl, or substituted aralkyl having from 1 to 20carbon atoms.

In each occurrence, arsenic groups are arsenic-containing groups, whichcan include, but are not limited to, —AsR^(X) ₂, —As(OR^(X))₂, and thelike, including substituted derivatives thereof, wherein R^(X) in eachoccurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl having from 1 to 20 carbonatoms.

In each occurrence, carbon groups are carbon-containing groups, whichcan include, but are not limited to, alkyl halide groups that comprisehalide-substituted alkyl groups with 1 to 20 carbon atoms, aralkylgroups with 1 to 20 carbon atoms, —C(NR^(X))H, —C(NR^(X))R^(X),—C(NR^(X))OR^(X), and the like, including substituted derivativesthereof, wherein R^(X) in each occurrence can be alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl having from 1 to 20 carbon atoms.

In each occurrence, silicon groups are silicon-containing groups, whichcan include, but are not limited to, silyl groups such as alkylsilylgroups, arylsilyl groups, arylalkylsilyl groups, siloxy groups, and thelike, which in each occurrence can have from 1 to 20 carbon atoms. Forexample, silicon group substituents can include trimethylsilyl andphenyloctylsilyl groups.

In each occurrence, germanium groups are germanium-containing groups,which can include, but are not limited to, germyl groups such asalkylgermyl groups, arylgermyl groups, arylalkylgermyl groups, germyloxygroups, and the like, which in each occurrence can have from 1 to 20carbon atoms.

In each occurrence, tin groups are tin-containing groups, which caninclude, but are not limited to, stannyl groups such as alkylstannylgroups, arylstannyl groups, arylalkylstannyl groups, stannoxy (or“stannyloxy”) groups, and the like, which in each occurrence can havefrom 1 to 20 carbon atoms. Thus, tin groups can include, but are notlimited to, stannoxy groups.

In each occurrence, lead groups are lead-containing groups, which caninclude, but are not limited to, alkyllead groups, aryllead groups,arylalkyllead groups, and the like, which in each occurrence, can havefrom 1 to 20 carbon atoms.

In each occurrence, boron groups are boron-containing groups, which caninclude, but are not limited to, —BR^(X) ₂, —BX₂, —BR^(X)X, and thelike, wherein X can be a monoanionic group such as hydride, alkoxide,alkyl thiolate, and the like, and wherein R^(X) in each occurrence canbe alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substitutedaryl, or substituted aralkyl having from 1 to 20 carbon atoms.

In each occurrence, aluminum groups are aluminum-containing groups,which can include, but are not limited to, —AlR^(X), —AlX₂, —AlR^(X)X,wherein X can be a monoanionic group such as hydride, alkoxide, alkylthiolate, and the like, and wherein R^(X) in each occurrence can bealkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl,or substituted aralkyl having from 1 to 20 carbon atoms.

Examples of inorganic groups that may be used as substituents, in eachoccurrence can include, but are not limited to, —OAlX₂, —OSiX₃, —OPX₂,—SX, —AsX₂, —PX₂, and the like, wherein X can be a monoanionic groupsuch as hydride, amide, alkoxide, alkyl thiolate, and the like, andwherein any alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl group or substituent on theseligands can have from 1 to 20 carbon atoms.

Examples of organometallic groups that may be used as substituents, ineach occurrence, can include, but are not limited to, organoborongroups, organoaluminum groups, organogallium groups, organosilicongroups, organogermanium groups, organotin groups, organolead groups,organo-transition metal groups, and the like, having from 1 to 20 carbonatoms.

In accordance with one aspect of the present invention, M can be Zr orTi in formula (I), and X¹ and X² independently can be a methyl group, aphenyl group, a benzyl group, or a halide. In this aspect, X³ can be asubstituted or unsubstituted cyclopentadienyl group, and X⁴ can be—O—R^(A). In these and other aspects, R^(A) can be a disubstituted arylgroup (e.g., a 2,6-disubstituted aryl group), one substituent of whichcan be a methoxy group, an ethoxy group, a propoxy group, or a butoxygroup; and the other substituent of which can be a methyl group, anethyl group, a propyl group, a n-butyl group, a t-butyl group, acyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group,a propoxy group, or a butoxy group.

In accordance with another aspect, M can be Zr or Ti in formula (I), andX¹ and X² independently can be a methyl group, a phenyl group, a benzylgroup, or a halide. In this aspect, X³ can be a substituted orunsubstituted cyclopentadienyl group, and X⁴ can be —O—Si—R^(B) ₃ or—O—C—R^(B) ₃. In these and other aspects, each R^(B) independently can amethyl group, an ethyl group, a propyl group, a n-butyl group, a t-butylgroup, a phenyl group, a benzyl group, a tolyl group, a xylyl group, amethyl benzyl group, a 1-ethenyl-2-phenyl group, or a 1-ethynyl-2-phenylgroup; alternatively, each R^(B) independently can be a phenyl group, abenzyl group, a tolyl group, a xylyl group, a methyl benzyl group, a1-ethenyl-2-phenyl group, or a 1-ethynyl-2-phenyl group.

In accordance with another aspect, hybrid metallocene compoundsdisclosed herein can have the formula:

wherein:

X¹ and X² independently can be a methyl group, a phenyl group, a benzylgroup, or a halide;

each R^(C) independently can be a hydrogen atom, a methyl group, anethyl group, a propyl group, a n-butyl group, a t-butyl group, or ahexyl group;

n can be an integer from 0 to 5, inclusive;

X⁴ can be —O—R^(A), —O—Si—R^(B) ₃, or —O—C—R^(B) ₃;

wherein:

-   -   R^(A) can be a 2,6-disubstituted aryl group, wherein the        substituent at the 2-position can be a methoxy group, an ethoxy        group, a propoxy group, or a butoxy group, and the substituent        at the 6-position can be a methyl group, an ethyl group, a        propyl group, a n-butyl group, a t-butyl group, a cyclopentyl        group, a cyclohexyl group, a methoxy group, an ethoxy group, a        propoxy group, or a butoxy group; and    -   each R^(B) independently can be a phenyl group, a benzyl group,        a tolyl group, a xylyl group, a methyl benzyl group, a        1-ethenyl-2-phenyl group, or a 1-ethynyl-2-phenyl group.

Yet, in accordance with another aspect, hybrid metallocene compoundsdisclosed herein can have the formula:

wherein:

each M independently can be Zr, Hf, or Ti;

each X¹ and X² independently can be a halide or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof;

each X³ independently can be a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, wherein any substituentson X³ independently can be a hydrogen atom or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof.

In particular aspects contemplated herein, M in formulas (III) and (IV)can be either Zr or Ti, or alternatively, M can be Ti. Each X¹ and X²independently can be any halide or any substituted or unsubstitutedaliphatic, aromatic, or cyclic group, or combination of groups,disclosed herein. For instance, each X¹ and X² independently can be amethyl group, a phenyl group, a benzyl group, or a halide. Additionally,each X³ independently can be a substituted or unsubstituted indenylgroup or, alternatively, each X³ independently can be a substituted orunsubstituted cyclopentadienyl group. In some aspects, X³ can beunsubstituted (e.g., an unsubstituted cyclopentadienyl group), while inother aspects, X³ can have one or more substituents. Any substituents onX³ independently can be a hydrogen atom or any substituted orunsubstituted aliphatic, aromatic, or cyclic group, or combination ofgroups, disclosed herein. As an example, each substituent on each X³independently can be a hydrogen atom, or a methyl, ethyl, propyl,n-butyl, t-butyl, or hexyl group.

Illustrative and non-limiting examples of hybrid metallocene compoundsof the present invention can include the following compounds:

and the like.

Other hybrid metallocene compounds are contemplated as being suitablefor use in the present invention, therefore, the scope of the presentinvention is not limited to the hybrid metallocene species providedabove.

Methods of making hybrid metallocene compounds of the present inventionalso are provided. In addition to the procedures employed in theExamples that follow, suitable methods can include those described inScholz et al., Journal of Organometallic Chemistry (1993), 443(1), 93-9;Thorn et al., Journal of the Chemical Society, Dalton Transactions(2002), 17, 3398-3405; and U.S. Patent Publication No. 2010-0010174; thedisclosures of which are incorporated herein by reference in theirentirety.

Activator-Support

The present invention encompasses various catalyst compositionscontaining an activator, which can be an activator-support. In oneaspect, the activator-support can comprise a chemically-treated solidoxide. Alternatively, the activator-support can comprise a clay mineral,a pillared clay, an exfoliated clay, an exfoliated clay gelled intoanother oxide matrix, a layered silicate mineral, a non-layered silicatemineral, a layered aluminosilicate mineral, a non-layeredaluminosilicate mineral, or combinations thereof.

Generally, chemically-treated solid oxides exhibit enhanced acidity ascompared to the corresponding untreated solid oxide compound. Thechemically-treated solid oxide also can function as a catalyst activatoras compared to the corresponding untreated solid oxide. While thechemically-treated solid oxide can activate the hybrid metallocene inthe absence of co-catalysts, it is not necessary to eliminateco-catalysts from the catalyst composition. The activation function ofthe activator-support may be evident in the enhanced activity ofcatalyst composition as a whole, as compared to a catalyst compositioncontaining the corresponding untreated solid oxide. However, it isbelieved that the chemically-treated solid oxide can function as anactivator, even in the absence of an organoaluminum compound,aluminoxanes, organoboron or organoborate compounds, ionizing ioniccompounds, and the like.

The chemically-treated solid oxide can comprise a solid oxide treatedwith an electron-withdrawing anion. While not intending to be bound bythe following statement, it is believed that treatment of the solidoxide with an electron-withdrawing component augments or enhances theacidity of the oxide. Thus, either the activator-support exhibits Lewisor Brønsted acidity that is typically greater than the Lewis or Brønstedacid strength of the untreated solid oxide, or the activator-support hasa greater number of acid sites than the untreated solid oxide, or both.One method to quantify the acidity of the chemically-treated anduntreated solid oxide materials can be by comparing the polymerizationactivities of the treated and untreated oxides under acid catalyzedreactions.

Chemically-treated solid oxides of this invention generally can beformed from an inorganic solid oxide that exhibits Lewis acidic orBrønsted acidic behavior and has a relatively high porosity. The solidoxide can be chemically-treated with an electron-withdrawing component,typically an electron-withdrawing anion, to form an activator-support.

According to one aspect of the present invention, the solid oxide usedto prepare the chemically-treated solid oxide can have a pore volumegreater than about 0.1 cc/g. According to another aspect of the presentinvention, the solid oxide can have a pore volume greater than about 0.5cc/g. According to yet another aspect of the present invention, thesolid oxide can have a pore volume greater than about 1.0 cc/g.

In another aspect, the solid oxide can have a surface area of from about100 to about 1000 m²/g. In yet another aspect, the solid oxide can havea surface area of from about 200 to about 800 m²/g. In still anotheraspect of the present invention, the solid oxide can have a surface areaof from about 250 to about 600 m²/g.

The chemically-treated solid oxide can comprise a solid inorganic oxidecomprising oxygen and one or more elements selected from Group 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, orcomprising oxygen and one or more elements selected from the lanthanideor actinide elements (See: Hawley's Condensed Chemical Dictionary,11^(th) Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G.,Murillo, C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6^(th)Ed., Wiley-Interscience, 1999). For example, the inorganic oxide cancomprise oxygen and an element, or elements, selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn, and Zr.

Suitable examples of solid oxide materials or compounds that can be usedto form the chemically-treated solid oxide can include, but are notlimited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃,Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂,TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixed oxidesthereof, and combinations thereof. For example, the solid oxide cancomprise silica, alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, titania,zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or anycombination thereof.

The solid oxide of this invention encompasses oxide materials such asalumina, “mixed oxide” compounds thereof such as silica-alumina, andcombinations and mixtures thereof. The mixed oxide compounds such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form a solid oxide compound. Examplesof mixed oxides that can be used in the activator-support of the presentinvention, either singly or in combination, can include, but are notlimited to, silica-alumina, silica-titania, silica-zirconia, zeolites,various clay minerals, alumina-titania, alumina-zirconia,zinc-aluminate, alumina-boria, silica-boria, aluminophosphate-silica,titania-zirconia, and the like. The solid oxide of this invention alsoencompasses oxide materials such as silica-coated alumina, as describedin U.S. Patent Publication No. 2010-0076167, the disclosure of which isincorporated herein by reference in its entirety.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspectof the present invention, the electron-withdrawing component can be anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anions caninclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, and the like, including mixtures andcombinations thereof. In addition, other ionic or non-ionic compoundsthat serve as sources for these electron-withdrawing anions also can beemployed in the present invention. It is contemplated that theelectron-withdrawing anion can be, or can comprise, fluoride, chloride,bromide, phosphate, triflate, bisulfate, or sulfate, and the like, orany combination thereof, in some aspects of this invention. In otheraspects, the electron-withdrawing anion can comprise sulfate, bisulfate,fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate,phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or combinations thereof.

Thus, for example, the activator-support (e.g., chemically-treated solidoxide) used in the catalyst compositions of the present invention canbe, or can comprise, fluorided alumina, chlorided alumina, bromidedalumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof.In one aspect, the activator-support can be, or can comprise, fluoridedalumina, sulfated alumina, fluorided silica-alumina, sulfatedsilica-alumina, fluorided silica-coated alumina, sulfated silica-coatedalumina, phosphated silica-coated alumina, and the like, or anycombination thereof. In another aspect, the activator-support cancomprise fluorided alumina; alternatively, chlorided alumina;alternatively, sulfated alumina; alternatively, fluoridedsilica-alumina; alternatively, sulfated silica-alumina; alternatively,fluorided silica-zirconia; alternatively, chlorided silica-zirconia; oralternatively, fluorided silica-coated alumina.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt can beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining. Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion can include, but are not limited to, the solubility of the salt inthe desired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion can include, but are not limited to,ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkylphosphonium, H⁺, [H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components can be contacted with the oxide materialsimultaneously or individually, and in any order that affords thedesired chemically-treated solid oxide acidity. For example, one aspectof this invention can employ two or more electron-withdrawing anionsource compounds in two or more separate contacting steps.

Thus, a process by which a chemically-treated solid oxide can beprepared is as follows: a selected solid oxide, or combination of solidoxides, can be contacted with a first electron-withdrawing anion sourcecompound to form a first mixture; this first mixture can be calcined andthen contacted with a second electron-withdrawing anion source compoundto form a second mixture; the second mixture then can be calcined toform a treated solid oxide. In such a process, the first and secondelectron-withdrawing anion source compounds can be either the same ordifferent compounds.

According to another aspect of the present invention, thechemically-treated solid oxide can comprise a solid inorganic oxidematerial, a mixed oxide material, or a combination of inorganic oxidematerials, that is chemically-treated with an electron-withdrawingcomponent, and optionally treated with a metal source, including metalsalts, metal ions, or other metal-containing compounds. Non-limitingexamples of the metal or metal ion can include zinc, nickel, vanadium,titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium,and the like, or combinations thereof. Examples of chemically-treatedsolid oxides that contain a metal or metal ion can include, but are notlimited to, chlorided zinc-impregnated alumina, fluoridedtitanium-impregnated alumina, fluorided zinc-impregnated alumina,chlorided zinc-impregnated silica-alumina, fluorided zinc-impregnatedsilica-alumina, sulfated zinc-impregnated alumina, chlorided zincaluminate, fluorided zinc aluminate, sulfated zinc aluminate,silica-coated alumina treated with hexafluorotitanic acid, silica-coatedalumina treated with zinc and then fluorided, and the like, or anycombination thereof.

Any method of impregnating the solid oxide material with a metal can beused. The method by which the oxide is contacted with a metal source,typically a salt or metal-containing compound, can include, but is notlimited to, gelling, co-gelling, impregnation of one compound ontoanother, and the like. If desired, the metal-containing compound can beadded to or impregnated into the solid oxide in solution form, andsubsequently converted into the supported metal upon calcining.Accordingly, the solid inorganic oxide can further comprise a metalselected from zinc, titanium, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, and the like, or combinations of thesemetals. For example, zinc often can be used to impregnate the solidoxide because it can provide improved catalyst activity at a low cost.

The solid oxide can be treated with metal salts or metal-containingcompounds before, after, or at the same time that the solid oxide istreated with the electron-withdrawing anion. Following any contactingmethod, the contacted mixture of solid compound, electron-withdrawinganion, and the metal ion can be calcined. Alternatively, a solid oxidematerial, an electron-withdrawing anion source, and the metal salt ormetal-containing compound can be contacted and calcined simultaneously.

Various processes can be used to form the chemically-treated solid oxideuseful in the present invention. The chemically-treated solid oxide cancomprise the contact product of one or more solid oxides with one ormore electron-withdrawing anion sources. It is not required that thesolid oxide be calcined prior to contacting the electron-withdrawinganion source. Typically, the contact product can be calcined eitherduring or after the solid oxide is contacted with theelectron-withdrawing anion source. The solid oxide can be calcined oruncalcined. Various processes to prepare solid oxide activator-supportsthat can be employed in this invention have been reported. For example,such methods are described in U.S. Pat. Nos. 6,107,230, 6,165,929,6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017,6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583,6,613,712, 6,632,894, 6,667,274, and 6,750,302, the disclosures of whichare incorporated herein by reference in their entirety.

According to one aspect of the present invention, the solid oxidematerial can be chemically-treated by contacting it with anelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material optionally can be chemicallytreated with a metal ion, and then calcined to form a metal-containingor metal-impregnated chemically-treated solid oxide. According toanother aspect of the present invention, the solid oxide material andelectron-withdrawing anion source can be contacted and calcinedsimultaneously.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include, but is not limited to, gelling, co-gelling, impregnation ofone compound onto another, and the like. Thus, following any contactingmethod, the contacted mixture of the solid oxide, electron-withdrawinganion, and optional metal ion, can be calcined.

The solid oxide activator-support (i.e., chemically-treated solid oxide)thus can be produced by a process comprising:

1) contacting a solid oxide (or solid oxides) with anelectron-withdrawing anion source compound (or compounds) to form afirst mixture; and

2) calcining the first mixture to form the solid oxideactivator-support.

According to another aspect of the present invention, the solid oxideactivator-support (chemically-treated solid oxide) can be produced by aprocess comprising:

1) contacting a solid oxide (or solid oxides) with a firstelectron-withdrawing anion source compound to form a first mixture;

2) calcining the first mixture to produce a calcined first mixture;

3) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and

4) calcining the second mixture to form the solid oxideactivator-support.

According to yet another aspect of the present invention, thechemically-treated solid oxide can be produced or formed by contactingthe solid oxide with the electron-withdrawing anion source compound,where the solid oxide compound is calcined before, during, or aftercontacting the electron-withdrawing anion source, and where there is asubstantial absence of aluminoxanes, organoboron or organoboratecompounds, and ionizing ionic compounds.

Calcining of the treated solid oxide generally can be conducted in anambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. Calcining can be conducted at a temperatureof from about 300° C. to about 800° C., or alternatively, at atemperature of from about 400° C. to about 700° C. Calcining can beconducted for about 30 minutes to about 50 hours, or for about 1 hour toabout 15 hours. Thus, for example, calcining can be carried out forabout 1 to about 10 hours at a temperature of from about 350° C. toabout 550° C. Any suitable ambient atmosphere can be employed duringcalcining. Generally, calcining can be conducted in an oxidizingatmosphere, such as air. Alternatively, an inert atmosphere, such asnitrogen or argon, or a reducing atmosphere, such as hydrogen or carbonmonoxide, can be used.

According to one aspect of the present invention, the solid oxidematerial can be treated with a source of halide ion, sulfate ion, or acombination of anions, optionally treated with a metal ion, and thencalcined to provide the chemically-treated solid oxide in the form of aparticulate solid. For example, the solid oxide material can be treatedwith a source of sulfate (termed a “sulfating agent”), a source ofchloride ion (termed a “chloriding agent”), a source of fluoride ion(termed a “fluoriding agent”), or a combination thereof, and calcined toprovide the solid oxide activator. Useful acidic activator-supports caninclude, but are not limited to, bromided alumina, chlorided alumina,fluorided alumina, sulfated alumina, bromided silica-alumina, chloridedsilica-alumina, fluorided silica-alumina, sulfated silica-alumina,bromided silica-zirconia, chlorided silica-zirconia, fluoridedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,alumina treated with hexafluorotitanic acid, silica-coated aluminatreated with hexafluorotitanic acid, silica-alumina treated withhexafluorozirconic acid, silica-alumina treated with trifluoroaceticacid, fluorided boria-alumina, silica treated with tetrafluoroboricacid, alumina treated with tetrafluoroboric acid, alumina treated withhexafluorophosphoric acid, a pillared clay, such as a pillaredmontmorillonite, optionally treated with fluoride, chloride, or sulfate;phosphated alumina or other aluminophosphates optionally treated withsulfate, fluoride, or chloride; or any combination of the above.Further, any of these activator-supports optionally can be treated orimpregnated with a metal ion.

The chemically-treated solid oxide can comprise a fluorided solid oxidein the form of a particulate solid. The fluorided solid oxide can beformed by contacting a solid oxide with a fluoriding agent. The fluorideion can be added to the oxide by forming a slurry of the oxide in asuitable solvent such as alcohol or water including, but not limited to,the one to three carbon alcohols because of their volatility and lowsurface tension. Examples of suitable fluoriding agents can include, butare not limited to, hydrofluoric acid (HF), ammonium fluoride (NH₄F),ammonium bifluoride (NH₄HF₂), ammonium tetrafluoroborate (NH₄BF₄),ammonium silicofluoride (hexafluorosilicate) ((NH₄)₂SiF₆), ammoniumhexafluorophosphate (NH₄PF₆), hexafluorotitanic acid (H₂TiF₆), ammoniumhexafluorotitanic acid ((NH₄)₂TiF₆), hexafluorozirconic acid (H₂ZrF₆),AlF₃, NH₄AlF₄, analogs thereof, and combinations thereof. Triflic acidand ammonium triflate also can be employed. For example, ammoniumbifluoride (NH₄HF₂) can be used as the fluoriding agent, due to its easeof use and availability.

If desired, the solid oxide can be treated with a fluoriding agentduring the calcining step. Any fluoriding agent capable of thoroughlycontacting the solid oxide during the calcining step can be used. Forexample, in addition to those fluoriding agents described previously,volatile organic fluoriding agents can be used. Examples of volatileorganic fluoriding agents useful in this aspect of the invention caninclude, but are not limited to, freons, perfluorohexane,perfluorobenzene, fluoromethane, trifluoroethanol, and the like, andcombinations thereof. Calcining temperatures generally must be highenough to decompose the compound and release fluoride. Gaseous hydrogenfluoride (HF) or fluorine (F₂) itself also can be used with the solidoxide if fluorided while calcining. Silicon tetrafluoride (SiF₄) andcompounds containing tetrafluoroborate (BF₄ ⁻) also can be employed. Oneconvenient method of contacting the solid oxide with the fluoridingagent can be to vaporize a fluoriding agent into a gas stream used tofluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide can comprise a chlorided solid oxide in the form of aparticulate solid. The chlorided solid oxide can be formed by contactinga solid oxide with a chloriding agent. The chloride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Thesolid oxide can be treated with a chloriding agent during the calciningstep. Any chloriding agent capable of serving as a source of chlorideand thoroughly contacting the oxide during the calcining step can beused, such as SiCl₄, SiMe₂Cl₂, TiCl₄, BCl₃, and the like, includingmixtures thereof. Volatile organic chloriding agents can be used.Examples of suitable volatile organic chloriding agents can include, butare not limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, andthe like, or any combination thereof. Gaseous hydrogen chloride orchlorine itself also can be used with the solid oxide during calcining.One convenient method of contacting the oxide with the chloriding agentcan be to vaporize a chloriding agent into a gas stream used to fluidizethe solid oxide during calcination.

The amount of fluoride or chloride ion present before calcining thesolid oxide generally can be from about 1 to about 50% by weight, wherethe weight percent is based on the weight of the solid oxide, forexample, silica-alumina, before calcining According to another aspect ofthis invention, the amount of fluoride or chloride ion present beforecalcining the solid oxide can be from about 1 to about 25% by weight,and according to another aspect of this invention, from about 2 to about20% by weight. According to yet another aspect of this invention, theamount of fluoride or chloride ion present before calcining the solidoxide can be from about 4 to about 10% by weight. Once impregnated withhalide, the halided oxide can be dried by any suitable method including,but not limited to, suction filtration followed by evaporation, dryingunder vacuum, spray drying, and the like, although it is also possibleto initiate the calcining step immediately without drying theimpregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina typicallycan have a pore volume greater than about 0.5 cc/g. According to oneaspect of the present invention, the pore volume can be greater thanabout 0.8 cc/g, and according to another aspect of the presentinvention, greater than about 1.0 cc/g. Further, the silica-aluminagenerally can have a surface area greater than about 100 m²/g. Accordingto another aspect of this invention, the surface area can be greaterthan about 250 m²/g. Yet, in another aspect, the surface area can begreater than about 350 m²/g.

The silica-alumina utilized in the present invention typically can havean alumina content from about 5 to about 95% by weight. According to oneaspect of this invention, the alumina content of the silica-alumina canbe from about 5 to about 50%, or from about 8% to about 30%, alumina byweight. In another aspect, high alumina content silica-alumina compoundscan be employed, in which the alumina content of these silica-aluminacompounds typically ranges from about 60% to about 90%, or from about65% to about 80%, alumina by weight. According to yet another aspect ofthis invention, the solid oxide component can comprise alumina withoutsilica, and according to another aspect of this invention, the solidoxide component can comprise silica without alumina.

The sulfated solid oxide can comprise sulfate and a solid oxidecomponent, such as alumina or silica-alumina, in the form of aparticulate solid. Optionally, the sulfated oxide can be treated furtherwith a metal ion such that the calcined sulfated oxide comprises ametal. According to one aspect of the present invention, the sulfatedsolid oxide can comprise sulfate and alumina. In some instances, thesulfated alumina can be formed by a process wherein the alumina istreated with a sulfate source, for example, sulfuric acid or a sulfatesalt such as ammonium sulfate. This process generally can be performedby forming a slurry of the alumina in a suitable solvent, such asalcohol or water, in which the desired concentration of the sulfatingagent has been added. Suitable organic solvents can include, but are notlimited to, the one to three carbon alcohols because of their volatilityand low surface tension.

According to one aspect of this invention, the amount of sulfate ionpresent before calcining can be from about 0.5 to about 100 parts byweight sulfate ion to about 100 parts by weight solid oxide. Accordingto another aspect of this invention, the amount of sulfate ion presentbefore calcining can be from about 1 to about 50 parts by weight sulfateion to about 100 parts by weight solid oxide, and according to stillanother aspect of this invention, from about 5 to about 30 parts byweight sulfate ion to about 100 parts by weight solid oxide. Theseweight ratios are based on the weight of the solid oxide beforecalcining. Once impregnated with sulfate, the sulfated oxide can bedried by any suitable method including, but not limited to, suctionfiltration followed by evaporation, drying under vacuum, spray drying,and the like, although it is also possible to initiate the calciningstep immediately.

According to another aspect of the present invention, theactivator-support used in preparing the catalyst compositions of thisinvention can comprise an ion-exchangeable activator-support including,but not limited to, silicate and aluminosilicate compounds or minerals,either with layered or non-layered structures, and combinations thereof.In another aspect of this invention, ion-exchangeable, layeredaluminosilicates such as pillared clays can be used asactivator-supports. When the acidic activator-support comprises anion-exchangeable activator-support, it can optionally be treated with atleast one electron-withdrawing anion such as those disclosed herein,though typically the ion-exchangeable activator-support is not treatedwith an electron-withdrawing anion.

According to another aspect of the present invention, theactivator-support of this invention can comprise clay minerals havingexchangeable cations and layers capable of expanding. Typical claymineral activator-supports can include, but are not limited to,ion-exchangeable, layered aluminosilicates such as pillared clays.Although the term “support” is used, it is not meant to be construed asan inert component of the catalyst composition, but rather can beconsidered an active part of the catalyst composition, because of itsintimate association with the hybrid metallocene component.

According to another aspect of the present invention, the clay materialsof this invention can encompass materials either in their natural stateor that have been treated with various ions by wetting, ion exchange, orpillaring. Typically, the clay material activator-support of thisinvention can comprise clays that have been ion exchanged with largecations, including polynuclear, highly charged metal complex cations.However, the clay material activator-supports of this invention also canencompass clays that have been ion exchanged with simple salts,including, but not limited to, salts of Al(III), Fe(II), Fe(III), andZn(II) with ligands such as halide, acetate, sulfate, nitrate, ornitrite.

According to another aspect of the present invention, theactivator-support can comprise a pillared clay. The term “pillared clay”is used to refer to clay materials that have been ion exchanged withlarge, typically polynuclear, highly charged metal complex cations.Examples of such ions can include, but are not limited to, Keggin ionswhich can have charges such as 7+, various polyoxometallates, and otherlarge ions. Thus, the term pillaring can refer to a simple exchangereaction in which the exchangeable cations of a clay material arereplaced with large, highly charged ions, such as Keggin ions. Thesepolymeric cations then can be immobilized within the interlayers of theclay and when calcined are converted to metal oxide “pillars,”effectively supporting the clay layers as column-like structures. Thus,once the clay is dried and calcined to produce the supporting pillarsbetween clay layers, the expanded lattice structure can be maintainedand the porosity can be enhanced. The resulting pores can vary in shapeand size as a function of the pillaring material and the parent claymaterial used. Examples of pillaring and pillared clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J. M. Thomas,Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3,pp. 55-99, Academic Press, Inc., (1972); U.S. Pat. No. 4,452,910; U.S.Pat. No. 5,376,611; and U.S. Pat. No. 4,060,480; the disclosures ofwhich are incorporated herein by reference in their entirety.

The pillaring process can utilize clay minerals having exchangeablecations and layers capable of expanding. Any pillared clay that canenhance the polymerization of olefins in the catalyst composition of thepresent invention can be used. Therefore, suitable clay minerals forpillaring can include, but are not limited to, allophanes; smectites,both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereofsuch as montmorillonites (bentonites), nontronites, hectorites, orlaponites; halloysites; vermiculites; micas; fluoromicas; chlorites;mixed-layer clays; the fibrous clays including but not limited tosepiolites, attapulgites, and palygorskites; a serpentine clay; illite;laponite; saponite; and any combination thereof. In one aspect, thepillared clay activator-support can comprise bentonite ormontmorillonite. The principal component of bentonite ismontmorillonite.

The pillared clay can be pretreated if desired. For example, a pillaredbentonite can be pretreated by drying at about 300° C. under an inertatmosphere, typically dry nitrogen, for about 3 hours, before beingadded to the polymerization reactor. Although an exemplary pretreatmentis described herein, it should be understood that the preheating can becarried out at many other temperatures and times, including anycombination of temperature and time steps, all of which are encompassedby this invention.

The activator-support used to prepare the catalyst compositions of thepresent invention can be combined with other inorganic supportmaterials, including, but not limited to, zeolites, inorganic oxides,phosphated inorganic oxides, and the like. In one aspect, typicalsupport materials that can be used include, but are not limited to,silica, silica-alumina, alumina, titania, zirconia, magnesia, boria,thoria, aluminophosphate, aluminum phosphate, silica-titania,coprecipitated silica/titania, mixtures thereof, or any combinationthereof.

According to another aspect of the present invention, one or more of thehybrid metallocene compounds can be precontacted with an olefin monomerand an organoaluminum compound for a first period of time prior tocontacting this mixture with the activator-support. Once theprecontacted mixture of the metallocene compound(s), olefin monomer, andorganoaluminum compound is contacted with the activator-support, thecomposition further comprising the activator-support is termed a“postcontacted” mixture. The postcontacted mixture can be allowed toremain in further contact for a second period of time prior to beingcharged into the reactor in which the polymerization process will becarried out.

According to yet another aspect of the present invention, one or more ofthe hybrid metallocene compounds can be precontacted with an olefinmonomer and an activator-support for a first period of time prior tocontacting this mixture with the organoaluminum compound. Once theprecontacted mixture of the metallocene compound(s), olefin monomer, andactivator-support is contacted with the organoaluminum compound, thecomposition further comprising the organoaluminum is termed a“postcontacted” mixture. The postcontacted mixture can be allowed toremain in further contact for a second period of time prior to beingintroduced into the polymerization reactor.

Organoaluminum Compounds

In some aspects, catalyst compositions of the present invention cancomprise one or more organoaluminum compounds. Such compounds caninclude, but are not limited to, compounds having the formula:(R¹)₃Al;where R¹ can be an aliphatic group having from 1 to 10 carbon atoms. Forexample, R¹ can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl.

Other organoaluminum compounds which can be used in catalystcompositions disclosed herein can include, but are not limited to,compounds having the formula:Al(X⁵)_(m)(X⁶)_(3−m),where X⁵ can be a hydrocarbyl; X⁶ can be an alkoxide or an aryloxide, ahalide, or a hydride; and m can be from 1 to 3, inclusive. Hydrocarbylis used herein to specify a hydrocarbon radical group and includes, butis not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl,cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like,and includes all substituted, unsubstituted, branched, linear, and/orheteroatom substituted derivatives thereof.

In one aspect, X⁵ can be a hydrocarbyl having from 1 to about 18 carbonatoms. In another aspect of the present invention, X⁵ can be an alkylhaving from 1 to 10 carbon atoms. For example, X⁵ can be methyl, ethyl,propyl, n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yetanother aspect of the present invention.

According to one aspect of the present invention, X⁶ can be an alkoxideor an aryloxide, any one of which has from 1 to 18 carbon atoms, ahalide, or a hydride. In another aspect of the present invention, X⁶ canbe selected independently from fluorine and chlorine. Yet, in anotheraspect, X⁶ can be chlorine.

In the formula, Al(X⁵)_(m)(X⁶)_(3−m), m can be a number from 1 to 3,inclusive, and typically, m can be 3. The value of m is not restrictedto be an integer; therefore, this formula can include sesquihalidecompounds or other organoaluminum cluster compounds.

Examples of organoaluminum compounds suitable for use in accordance withthe present invention can include, but are not limited to,trialkylaluminum compounds, dialkylaluminum halide compounds,dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds,and combinations thereof. Specific non-limiting examples of suitableorganoaluminum compounds can include trimethylaluminum (TMA),triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum(TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof.

The present invention contemplates a method of precontacting a hybridmetallocene compound with an organoaluminum compound and an olefinmonomer to form a precontacted mixture, prior to contacting thisprecontacted mixture with an activator-support to form a catalystcomposition. When the catalyst composition is prepared in this manner,typically, though not necessarily, a portion of the organoaluminumcompound can be added to the precontacted mixture and another portion ofthe organoaluminum compound can be added to the postcontacted mixtureprepared when the precontacted mixture is contacted with the solid oxideactivator-support. However, the entire organoaluminum compound can beused to prepare the catalyst composition in either the precontacting orpostcontacting step. Alternatively, all the catalyst components can becontacted in a single step.

Further, more than one organoaluminum compound can be used in either theprecontacting or the postcontacting step. When an organoaluminumcompound is added in multiple steps, the amounts of organoaluminumcompound disclosed herein include the total amount of organoaluminumcompound used in both the precontacted and postcontacted mixtures, andany additional organoaluminum compound added to the polymerizationreactor. Therefore, total amounts of organoaluminum compounds aredisclosed regardless of whether a single organoaluminum compound or morethan one organoaluminum compound is used.

Aluminoxane Compounds

The present invention further provides a catalyst composition which cancomprise an aluminoxane compound. As used herein, the term “aluminoxane”refers to aluminoxane compounds, compositions, mixtures, or discretespecies, regardless of how such aluminoxanes are prepared, formed orotherwise provided. For example, a catalyst composition comprising analuminoxane compound can be prepared in which aluminoxane is provided asthe poly(hydrocarbyl aluminum oxide), or in which aluminoxane isprovided as the combination of an aluminum alkyl compound and a sourceof active protons such as water. Aluminoxanes also can be referred to aspoly(hydrocarbyl aluminum oxides) or organoaluminoxanes.

The other catalyst components typically can be contacted with thealuminoxane in a saturated hydrocarbon compound solvent, though anysolvent that is substantially inert to the reactants, intermediates, andproducts of the activation step can be used. The catalyst compositionformed in this manner can be collected by any suitable method, forexample, by filtration. Alternatively, the catalyst composition can beintroduced into the polymerization reactor without being isolated.

The aluminoxane compound of this invention can be an oligomeric aluminumcompound comprising linear structures, cyclic structures, or cagestructures, or mixtures of all three. Cyclic aluminoxane compoundshaving the formula:

wherein R in this formula can be a linear or branched alkyl having from1 to 10 carbon atoms, and p in this formula can be an integer from 3 to20, are encompassed by this invention. The AlRO moiety shown here alsocan constitute the repeating unit in a linear aluminoxane. Thus, linearaluminoxanes having the formula:

wherein R in this formula can be a linear or branched alkyl having from1 to 10 carbon atoms, and q in this formula can be an integer from 1 to50, are also encompassed by this invention.

Further, aluminoxanes can have cage structures of the formula R^(t)_(5r+α)R^(b) _(r−α)Al_(4r)O_(3r), wherein R^(t) can be a terminal linearor branched alkyl group having from 1 to 10 carbon atoms; R^(b) can be abridging linear or branched alkyl group having from 1 to 10 carbonatoms; r can be 3 or 4; and α can be equal ton_(Al(3))−n_(O(2))+n_(O(4)), wherein n_(Al(3)) is the number of threecoordinate aluminum atoms, n_(O(2)) is the number of two coordinateoxygen atoms, and n_(O(4)) is the number of 4 coordinate oxygen atoms.

Thus, aluminoxanes which can be employed in the catalyst compositions ofthe present invention can be represented generally by formulas such as(R—Al—O)_(p), R(R—Al—O)_(q)AlR₂, and the like. In these formulas, the Rgroup typically can be a linear or branched C₁-C₆ alkyl, such as methyl,ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxanecompounds that can be used in accordance with the present invention caninclude, but are not limited to, methylaluminoxane, ethylaluminoxane,n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,isopentylaluminoxane, neopentylaluminoxane, and the like, or anycombination thereof. Methylaluminoxane, ethylaluminoxane, andiso-butylaluminoxane can be prepared from trimethylaluminum,triethylaluminum, or triisobutylaluminum, respectively, and sometimesare referred to as poly(methyl aluminum oxide), poly(ethyl aluminumoxide), and poly(isobutyl aluminum oxide), respectively. It is alsowithin the scope of the invention to use an aluminoxane in combinationwith a trialkylaluminum, such as that disclosed in U.S. Pat. No.4,794,096, incorporated herein by reference in its entirety.

The present invention contemplates many values of p and q in thealuminoxane formulas (R—Al—O)_(p) and R(R—Al—O)_(q)AlR₂, respectively.In some aspects, p and q can be at least 3. However, depending upon howthe organoaluminoxane is prepared, stored, and used, the value of p andq can vary within a single sample of aluminoxane, and such combinationsof organoaluminoxanes are contemplated herein.

In preparing a catalyst composition containing an aluminoxane, the molarratio of the total moles of aluminum in the aluminoxane (oraluminoxanes) to the total moles of metallocene compound(s) in thecomposition generally can be between about 1:10 and about 100,000:1. Inanother aspect, the molar ratio can be in a range from about 5:1 toabout 15,000:1. Optionally, aluminoxane can be added to a polymerizationzone in ranges from about 0.01 mg/L to about 1000 mg/L, from about 0.1mg/L to about 100 mg/L, or from about 1 mg/L to about 50 mg/L.

Organoaluminoxanes can be prepared by various procedures. Examples oforganoaluminoxane preparations are disclosed in U.S. Pat. Nos. 3,242,099and 4,808,561, the disclosures of which are incorporated herein byreference in their entirety. For example, water in an inert organicsolvent can be reacted with an aluminum alkyl compound, such as (R¹)₃Al,to form the desired organoaluminoxane compound. While not intending tobe bound by this statement, it is believed that this synthetic methodcan afford a mixture of both linear and cyclic R—Al—O aluminoxanespecies, both of which are encompassed by this invention. Alternatively,organoaluminoxanes can be prepared by reacting an aluminum alkylcompound, such as (R¹)₃Al, with a hydrated salt, such as hydrated coppersulfate, in an inert organic solvent.

Organoboron/Organoborate Compounds

According to another aspect of the present invention, the catalystcomposition can comprise an organoboron or organoborate compound. Suchcompounds can include neutral boron compounds, borate salts, and thelike, or combinations thereof. For example, fluoroorgano boron compoundsand fluoroorgano borate compounds are contemplated.

Any fluoroorgano boron or fluoroorgano borate compound can be utilizedwith the present invention. Examples of fluoroorgano borate compoundsthat can be used in the present invention can include, but are notlimited to, fluorinated aryl borates such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, ormixtures thereof. Examples of fluoroorgano boron compounds that can beused as co-catalysts or activators in the present invention can include,but are not limited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or mixturesthereof. Although not intending to be bound by the following theory,these examples of fluoroorgano borate and fluoroorgano boron compounds,and related compounds, are thought to form “weakly-coordinating” anionswhen combined with hybrid metallocene compounds, as disclosed in U.S.Pat. No. 5,919,983, the disclosure of which is incorporated herein byreference in its entirety. Applicants also contemplate the use ofdiboron, or bis-boron, compounds or other bifunctional compoundscontaining two or more boron atoms in the chemical structure, such asdisclosed in J. Am. Chem. Soc., 2005, 127, pp. 14756-14768, the contentof which is incorporated herein by reference in its entirety.

Generally, any amount of organoboron compound can be used. According toone aspect of this invention, the molar ratio of the total moles oforganoboron or organoborate compound (or compounds) to the total molesof hybrid metallocene compound (or compounds) in the catalystcomposition can be in a range from about 0.1:1 to about 15:1. Typically,the amount of the fluoroorgano boron or fluoroorgano borate compoundused can be from about 0.5 moles to about 10 moles of boron/boratecompound per mole of hybrid metallocene compound(s). According toanother aspect of this invention, the amount of fluoroorgano boron orfluoroorgano borate compound can be from about 0.8 moles to about 5moles of boron/borate compound per mole of hybrid metallocenecompound(s).

Ionizing Ionic Compounds

The present invention further provides a catalyst composition which cancomprise an ionizing ionic compound. An ionizing ionic compound is anionic compound that can function as an activator or co-catalyst toenhance the activity of the catalyst composition. While not intending tobe bound by theory, it is believed that the ionizing ionic compound iscapable of reacting with a hybrid metallocene compound and convertingthe metallocene into one or more cationic metallocene compounds, orincipient cationic metallocene compounds. Again, while not intending tobe bound by theory, it is believed that the ionizing ionic compound canfunction as an ionizing compound by completely or partially extractingan anionic ligand, possibly a non-alkadienyl ligand such as X¹ or X²,from the hybrid metallocene. However, the ionizing ionic compound can bean activator or co-catalyst regardless of whether it is ionizes thehybrid metallocene, abstracts a X¹ or X² ligand in a fashion as to forman ion pair, weakens the metal-X¹ or metal-X² bond in the hybridmetallocene, simply coordinates to a X¹ or X² ligand, or activates thehybrid metallocene compound by some other mechanism.

Further, it is not necessary that the ionizing ionic compound activatethe hybrid metallocene compound only. The activation function of theionizing ionic compound can be evident in the enhanced activity ofcatalyst composition as a whole, as compared to a catalyst compositionthat does not contain an ionizing ionic compound.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethyl-phenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,and the like, or combinations thereof. Ionizing ionic compounds usefulin this invention are not limited to these; other examples of ionizingionic compounds are disclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938,the disclosures of which are incorporated herein by reference in theirentirety.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described above. Styrene can also be employedas a monomer in the present invention. In an aspect, the olefin monomercan be a C₂-C₁₀ olefin; alternatively, the olefin monomer can beethylene; or alternatively, the olefin monomer can be propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer can comprise, for example, ethylene or propylene, which iscopolymerized with at least one comonomer. According to one aspect ofthis invention, the olefin monomer in the polymerization process cancomprise ethylene. In this aspect, examples of suitable olefincomonomers an include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene,styrene, and the like, or combinations thereof. According to one aspectof the present invention, the comonomer can comprise 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combinationthereof.

Generally, the amount of comonomer introduced into a reactor zone toproduce a copolymer can be from about 0.01 to about 50 weight percent ofthe comonomer based on the total weight of the monomer and comonomer.According to another aspect of the present invention, the amount ofcomonomer introduced into a reactor zone can be from about 0.01 to about40 weight percent comonomer based on the total weight of the monomer andcomonomer. In still another aspect, the amount of comonomer introducedinto a reactor zone can be from about 0.1 to about 35 weight percentcomonomer based on the total weight of the monomer and comonomer. Yet,in another aspect, the amount of comonomer introduced into a reactorzone can be from about 0.5 to about 20 weight percent comonomer based onthe total weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight. According to one aspect of the present invention, at least onemonomer/reactant can be ethylene, so the polymerizations are either ahomopolymerization involving only ethylene, or copolymerizations with adifferent acyclic, cyclic, terminal, internal, linear, branched,substituted, or unsubstituted olefin. In addition, the catalystcompositions of this invention can be used in the polymerization ofdiolefin compounds including, but not limited to, 1,3-butadiene,isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Catalyst Compositions

In some aspects, the present invention employs catalyst compositionscontaining a hybrid metallocene having a heteroatom-containing ligandand an activator, while in other aspects, the present invention employscatalyst compositions containing a hybrid metallocene having aheteroatom-containing ligand and an activator-support. These catalystcompositions can be utilized to produce polyolefins—homopolymers,copolymers, and the like—for a variety of end-use applications.

Hybrid metallocene compounds having formulas (I), (II), (III), and (IV)were discussed above. In aspects of the present invention, it iscontemplated that the catalyst composition can contain more than onehybrid metallocene compound. Further, additional metallocenecompounds—other than those having formulas (I), (II), (III), and/or(IV)—can be employed in the catalyst composition and/or thepolymerization process, provided that the additional metallocenecompound(s) does not detract from the advantages disclosed herein.Additionally, more than one activator and/or more than oneactivator-support also may be utilized.

Generally, catalyst compositions of the present invention can comprise ahybrid metallocene compound having formula (I), (II), (III), and/or (IV)and an activator. In aspects of the invention, the activator cancomprise an activator-support. Activator-supports useful in the presentinvention were disclosed above. Such catalyst compositions can furthercomprise one or more than one organoaluminum compound or compounds(suitable organoaluminum compounds also were discussed above). Thus, acatalyst composition of this invention can comprise a hybrid metallocenecompound having formula (I), (II), (III), and/or (IV), anactivator-support, and an organoaluminum compound. For instance, theactivator-support can comprise (or consist essentially of, or consistof) fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof. Additionally, theorganoaluminum compound can comprise (or consist essentially of, orconsist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof. Accordingly, a catalyst composition consistent with thisinvention can comprise (or consist essentially of, or consist of) ahybrid metallocene compound having formula (I), (II), (III), and/or(IV), sulfated alumina (or fluorided silica-alumina), andtriethylaluminum (or triisobutylaluminum).

In another aspect of the present invention, a catalyst composition isprovided which comprises a hybrid metallocene compound having formula(I), (II), (III), and/or (IV), an activator-support, and anorganoaluminum compound, wherein this catalyst composition issubstantially free of aluminoxanes, organoboron or organoboratecompounds, ionizing ionic compounds, and/or other similar materials;alternatively, substantially free of aluminoxanes; alternatively,substantially free or organoboron or organoborate compounds; oralternatively, substantially free of ionizing ionic compounds. In theseaspects, the catalyst composition has catalyst activity, to be discussedbelow, in the absence of these additional materials. For example, acatalyst composition of the present invention can consist essentially ofa metallocene compound having formula (I), (II), (III), and/or (IV), anactivator-support, and an organoaluminum compound, wherein no othermaterials are present in the catalyst composition which wouldincrease/decrease the activity of the catalyst composition by more thanabout 10% from the catalyst activity of the catalyst composition in theabsence of said materials.

However, in other aspects of this invention, theseactivators/co-catalysts can be employed. For example, a catalystcomposition comprising a hybrid metallocene compound having formula (I),(II), (III), and/or (IV), and an activator-support can further comprisean optional co-catalyst. Suitable co-catalysts in this aspect include,but are not limited to, aluminoxane compounds, organoboron ororganoborate compounds, ionizing ionic compounds, and the like, or anycombination thereof. More than one co-catalyst can be present in thecatalyst composition.

In a different aspect, a catalyst composition is provided which does notrequire an activator-support. Such a catalyst composition can comprise ahybrid metallocene compound having formula (I), (II), (III), and/or(IV), and an activator, wherein the activator comprises an aluminoxanecompound, an organoboron or organoborate compound, an ionizing ioniccompound, or combinations thereof.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence.

The hybrid metallocene compound having formula (I), (II), (III), and/or(IV) can be precontacted with an olefinic monomer if desired, notnecessarily the olefin monomer to be polymerized, and an organoaluminumcompound for a first period of time prior to contacting thisprecontacted mixture with an activator-support. The first period of timefor contact, the precontact time, between the metallocene compound, theolefinic monomer, and the organoaluminum compound typically ranges froma time period of about 1 minute to about 24 hours, for example, fromabout 3 minutes to about 1 hour. Precontact times from about 10 minutesto about 30 minutes are also employed. Alternatively, the precontactingprocess is carried out in multiple steps, rather than a single step, inwhich multiple mixtures are prepared, each comprising a different set ofcatalyst components. For example, at least two catalyst components arecontacted forming a first mixture, followed by contacting the firstmixture with at least one other catalyst component forming a secondmixture, and so forth.

Multiple precontacting steps can be carried out in a single vessel or inmultiple vessels. Further, multiple precontacting steps can be carriedout in series (sequentially), in parallel, or a combination thereof. Forexample, a first mixture of two catalyst components can be formed in afirst vessel, a second mixture comprising the first mixture plus oneadditional catalyst component can be formed in the first vessel or in asecond vessel, which is typically placed downstream of the first vessel.

In another aspect, one or more of the catalyst components can be splitand used in different precontacting treatments. For example, part of acatalyst component is fed into a first precontacting vessel forprecontacting with at least one other catalyst component, while theremainder of that same catalyst component is fed into a secondprecontacting vessel for precontacting with at least one other catalystcomponent, or is fed directly into the reactor, or a combinationthereof. The precontacting can be carried out in any suitable equipment,such as tanks, stirred mix tanks, various static mixing devices, aflask, a vessel of any type, or combinations of these apparatus.

In another aspect of this invention, the various catalyst components(for example, a hybrid metallocene compound having formula (I), (II),(III), and/or (IV), activator-support, organoaluminum co-catalyst, andoptionally an unsaturated hydrocarbon) can be contacted in thepolymerization reactor simultaneously while the polymerization reactionis proceeding. Alternatively, any two or more of these catalystcomponents can be precontacted in a vessel prior to entering thereaction zone. This precontacting step can be continuous, in which theprecontacted product is fed continuously to the reactor, or it can be astepwise or batchwise process in which a batch of precontacted productis added to make a catalyst composition. This precontacting step can becarried out over a time period that can range from a few seconds to asmuch as several days, or longer. In this aspect, the continuousprecontacting step generally lasts from about 1 second to about 1 hour.In another aspect, the continuous precontacting step lasts from about 10seconds to about 45 minutes, or from about 1 minute to about 30 minutes.

Once the precontacted mixture of the metallocene compound having formula(I), (II), (III), and/or (IV), the olefin monomer, and theorganoaluminum co-catalyst is contacted with the activator-support, thiscomposition (with the addition of the activator-support) is termed the“postcontacted mixture.” The postcontacted mixture optionally can remainin contact for a second period of time, the postcontact time, prior toinitiating the polymerization process. Postcontact times between theprecontacted mixture and the activator-support generally range fromabout 1 minute to about 24 hours. In a further aspect, the postcontacttime is in a range from about 3 minutes to about 1 hour. Theprecontacting step, the postcontacting step, or both, can increase theproductivity of the polymer as compared to the same catalyst compositionthat is prepared without precontacting or postcontacting. However,neither a precontacting step nor a postcontacting step is required.

The postcontacted mixture can be heated at a temperature and for a timeperiod sufficient to allow adsorption, impregnation, or interaction ofprecontacted mixture and the activator-support, such that a portion ofthe components of the precontacted mixture is immobilized, adsorbed, ordeposited thereon. Where heating is employed, the postcontacted mixturegenerally is heated to a temperature of from between about −15° C. toabout 70° C., or from about 0° C. to about 40° C.

When a precontacting step is used, the molar ratio of the total moles ofolefin monomer to total moles of metallocene(s) in the precontactedmixture typically can be in a range from about 1:10 to about 100,000:1.Total moles of each component are used in this ratio to account foraspects of this invention where more than one olefin monomer and/or morethan one metallocene compound is employed in a precontacting step.Further, this molar ratio can be in a range from about 10:1 to about1,000:1 in another aspect of the invention.

Generally, the weight ratio of organoaluminum compound toactivator-support can be in a range from about 10:1 to about 1:1000. Ifmore than one organoaluminum compound and/or more than oneactivator-support is employed, this ratio is based on the total weightof each respective component. In another aspect, the weight ratio of theorganoaluminum compound to the activator-support can be in a range fromabout 3:1 to about 1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of metallocenecompound(s) to activator-support can be in a range from about 1:1 toabout 1:1,000,000. If more than one activator-support is employed, thisratio is based on the total weight of the activator-support. In anotheraspect, this weight ratio can be in a range from about 1:5 to about1:100,000, or from about 1:10 to about 1:10,000. Yet, in another aspect,the weight ratio of the metallocene compound(s) to the activator-supportcan be in a range from about 1:20 to about 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 100 grams of polyethylene (homopolymer,copolymer, etc., as the context requires) per gram of activator-supportper hour (abbreviated g/g/hr). In another aspect, the catalyst activitycan be greater than about 150, greater than about 250, or greater thanabout 500 g/g/hr. In still another aspect, catalyst compositions of thisinvention can be characterized by having a catalyst activity greaterthan about 550, greater than about 650, or greater than about 750g/g/hr. Yet, in another aspect, the catalyst activity can be greaterthan about 1000 g/g/hr. This activity is measured under slurrypolymerization conditions using isobutane as the diluent, at apolymerization temperature of about 90° C. and a reactor pressure ofabout 400 psig (2.75 MPa).

In accordance with another aspect of the present invention, catalystcompositions disclosed herein can have a catalyst activity greater thanabout 500 kilograms of polyethylene (homopolymer, copolymer, etc., asthe context requires) per mol of metallocene per hour (abbreviatedkg/mol/hr). In another aspect, the catalyst activity of the catalystcomposition can be greater than about 1000, greater than about 2000, orgreater than about 3000 kg/mol/hr. In still another aspect, catalystcompositions of this invention can be characterized by having a catalystactivity greater than about 5000, greater than about 8000, or greaterthan about 10,000 kg/mol/hr. Yet, in another aspect, the catalystactivity can be greater than about 15,000 kg/mol/hr. This activity ismeasured under slurry polymerization conditions using isobutane as thediluent, at a polymerization temperature of about 90° C. and a reactorpressure of about 400 psig (2.75 MPa).

As discussed above, any combination of the metallocene compound havingformula (I), (II), (III), and/or (IV), the activator-support, theorganoaluminum compound, and the olefin monomer, can be precontacted insome aspects of this invention. When any precontacting occurs with anolefinic monomer, it is not necessary that the olefin monomer used inthe precontacting step be the same as the olefin to be polymerized.Further, when a precontacting step among any combination of the catalystcomponents is employed for a first period of time, this precontactedmixture can be used in a subsequent postcontacting step between anyother combination of catalyst components for a second period of time.For example, the metallocene compound, the organoaluminum compound, and1-hexene can be used in a precontacting step for a first period of time,and this precontacted mixture then can be contacted with theactivator-support to form a postcontacted mixture that is contacted fora second period of time prior to initiating the polymerization reaction.For example, the first period of time for contact, the precontact time,between any combination of the metallocene compound, the olefinicmonomer, the activator-support, and the organoaluminum compound can befrom about 1 minute to about 24 hours, from about 3 minutes to about 1hour, or from about 10 minutes to about 30 minutes. The postcontactedmixture optionally is allowed to remain in contact for a second periodof time, the postcontact time, prior to initiating the polymerizationprocess. According to one aspect of this invention, postcontact timesbetween the precontacted mixture and any remaining catalyst componentsis from about 1 minute to about 24 hours, or from about 5 minutes toabout 1 hour.

Polymerization Process

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention can comprise contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) under polymerization conditions to produce anolefin polymer, wherein the catalyst composition can comprise ametallocene compound having formula (I), (II), (III), and/or (IV), andan activator. Metallocene compounds having formula (I), (II), (III),and/or (IV), were discussed above.

In accordance with one aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising a hybridmetallocene compound having formula (I), (II), (III), and/or (IV), andan activator, wherein the activator comprises an activator-support.Activator-supports useful in the polymerization processes of the presentinvention were disclosed above. The catalyst composition can furthercomprise one or more than one organoaluminum compound or compounds(suitable organoaluminum compounds also were discussed above). Thus, aprocess for polymerizing olefins in the presence of a catalystcomposition can employ a catalyst composition comprising a hybridmetallocene compound having formula (I), (II), (III), and/or (IV), anactivator-support, and an organoaluminum compound. In some aspects, theactivator-support can comprise (or consist essentially of, or consistof) fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof. In some aspects, theorganoaluminum compound can comprise (or consist essentially of, orconsist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising a hybridmetallocene compound having formula (I), (II), (III), and/or (IV), andan activator, wherein the activator comprises an aluminoxane compound,an organoboron or organoborate compound, an ionizing ionic compound, orcombinations thereof.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactors. As used herein, “polymerization reactor” includes anypolymerization reactor capable of polymerizing olefin monomers andcomonomers (one or more than one comonomer) to produce homopolymers,copolymers, terpolymers, and the like. The various types of reactorsinclude those that may be referred to as a batch reactor, slurryreactor, gas-phase reactor, solution reactor, high pressure reactor,tubular reactor, autoclave reactor, and the like, or combinationsthereof. The polymerization conditions for the various reactor types arewell known to those of skill in the art. Gas phase reactors may comprisefluidized bed reactors or staged horizontal reactors. Slurry reactorsmay comprise vertical or horizontal loops. High pressure reactors maycomprise autoclave or tubular reactors. Reactor types can include batchor continuous processes. Continuous processes could use intermittent orcontinuous product discharge. Processes may also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention may comprise onetype of reactor in a system or multiple reactors of the same ordifferent type. Production of polymers in multiple reactors may includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorsmay be different from the operating conditions of the other reactors.Alternatively, polymerization in multiple reactors may include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems may include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors maybe operated in series, in parallel, or both.

According to one aspect of the invention, the polymerization reactorsystem may comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer may becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes may comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent may beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies may be used forthis separation step including but not limited to, flashing that mayinclude any combination of heat addition and pressure reduction;separation by cyclonic action in either a cyclone or hydrocyclone; orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor may comprise at least one gas phase reactor. Such systems mayemploy a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream may bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product may be withdrawn from the reactor andnew or fresh monomer may be added to replace the polymerized monomer.Such gas phase reactors may comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor may comprise a tubular reactor or an autoclavereactor. Tubular reactors may have several zones where fresh monomer,initiators, or catalysts are added. Monomer may be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components may be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamsmay be intermixed for polymerization. Heat and pressure may be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor may comprise a solution polymerization reactor wherein themonomer/comonomer are contacted with the catalyst composition bysuitable stirring or other means. A carrier comprising an inert organicdiluent or excess monomer may be employed. If desired, themonomer/comonomer may be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation may be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactors suitable for the present invention may furthercomprise any combination of at least one raw material feed system, atleast one feed system for catalyst or catalyst components, and/or atleast one polymer recovery system. Suitable reactor systems for thepresent invention may further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature maybe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 110° C.,depending upon the type of polymerization reactor. In some reactorsystems, the polymerization temperature generally is within a range fromabout 70° C. to about 90° C., or from about 75° C. to about 85° C.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 to 3.4MPa). High pressure polymerization in tubular or autoclave reactors isgenerally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) may offer advantages.

Aspects of this invention are directed to olefin polymerizationprocesses comprising contacting a catalyst composition with an olefinmonomer and optionally an olefin comonomer under polymerizationconditions to produce an olefin polymer. The olefin polymer produced bythe process can have less than about 0.002 long chain branches per 1000total carbon atoms, and/or a ratio of Mw/Mn in a range from about 3 toabout 20, and/or a ratio of vinyl end groups to saturated end groups ina range from about 0.4 to about 0.9. In addition, or alternatively, theolefin polymer can have a melt index less than 2.5, and/or a Mn in arange from about 15,000 to about 50,000, and/or a Mw in a range fromabout 100,000 to about 300,000, and/or a Mz in a range from about750,000 to about 3,500,000, and/or a Mw/Mn in a range from about 5 toabout 15, and/or less than about 0.001 long chain branches per 1000total carbon atoms.

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. In thisdisclosure, “added hydrogen” will be denoted as the feed ratio ofhydrogen to olefin monomer entering the reactor (in units of ppm). Anolefin polymerization process of this invention can comprise contactinga catalyst composition with an olefin monomer and optionally an olefincomonomer under polymerization conditions to produce an olefin polymer,wherein the catalyst composition comprises a hybrid metallocene compoundand an activator, wherein the polymerization process is conducted in theabsence of added hydrogen. As disclosed above, the hybrid metallocenecan have formula (I), formula (II), formula (III), and/or formula (IV).As one of ordinary skill in the art would recognize, hydrogen can begenerated in-situ by metallocene catalyst compositions in various olefinpolymerization processes, and the amount generated may vary dependingupon the specific catalyst composition and metallocene compound(s)employed, the type of polymerization process used, the polymerizationreaction conditions utilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition with an olefin monomer andoptionally an olefin comonomer under polymerization conditions toproduce an olefin polymer, wherein the catalyst composition comprises ahybrid metallocene compound and an activator, wherein the polymerizationprocess is conducted in the presence of added hydrogen. For example, theratio of hydrogen to the olefin monomer in the polymerization processcan be controlled, often by the feed ratio of hydrogen to the olefinmonomer entering the reactor. The added hydrogen to olefin monomer ratioin the process can be controlled at a weight ratio which falls within arange from about 25 ppm to about 1500 ppm, from about 50 to about 1000ppm, or from about 100 ppm to about 750 ppm.

In some aspects of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorcan be controlled to produce resins with certain physical and mechanicalproperties. The proposed end-use product that will be formed by thepolymer resin and the method of forming that product ultimately candetermine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymersproduced by any of the polymerization processes disclosed herein.Articles of manufacture can be formed from, and/or can comprise, thepolymers produced in accordance with this invention.

Polymers and Articles

If the resultant polymer produced in accordance with the presentinvention is, for example, a polymer or copolymer of ethylene, itsproperties can be characterized by various analytical techniques knownand used in the polyolefin industry. Articles of manufacture can beformed from, and/or can comprise, the ethylene polymers of thisinvention, whose typical properties are provided below.

Polymers of ethylene (copolymers, terpolymers, etc.) produced inaccordance with this invention generally can have a melt index from 0 toabout 100 g/10 min. Melt indices in the range from 0 to about 75 g/10min, from 0 to about 50 g/10 min, or from 0 to about 30 g/10 min, arecontemplated in some aspects of this invention. For example, a polymerof the present invention can have a melt index (MI) in a range from 0 toabout 25, from 0 to about 10, from 0 to about 5, from 0 to about 2, orfrom 0 to about 1 g/10 min.

Ethylene polymers produced in accordance with this invention can have aratio of HLMI/MI of greater than about 25, such as, for example, greaterthan about 30, greater than about 40, or greater than about 50.Contemplated ranges for HLMI/MI include, but are not limited to, fromabout 50 to about 5000, from about 50 to about 4000, from about 50 toabout 3000, from about 75 to about 3000, or from about 75 to about 2750.

The density of ethylene-based polymers produced using one or more hybridmetallocene compounds of the present invention typically can fall withinthe range from about 0.88 to about 0.97 g/cc. In one aspect of thisinvention, the polymer density can be in a range from about 0.90 toabout 0.97 g/cc. Yet, in another aspect, the density generally can be ina range from about 0.91 to about 0.96 g/cc.

Ethylene polymers, such as copolymers and terpolymers, within the scopeof the present invention generally can have a polydispersity index—aratio of the weight-average molecular weight (Mw) to the number-averagemolecular weight (Mn)—in a range from about 3 to about 20. In someaspects disclosed herein, the ratio of Mw/Mn can be in a range fromabout 3.5 to about 20, from about 4 to about 20, from about 4 to about18, from about 5 to about 18, from about 5 to about 16, from about 5 toabout 14, from about 6 to about 14, or from about 6 to about 13.

The ratio of Mz/Mw for the polymers of this invention often can be in arange from about 3 to about 20. Mz is the z-average molecular weight. Inaccordance with one aspect, the Mz/Mw of the ethylene polymers of thisinvention can be in a range from about 3.5 to about 20, from about 4 toabout 20, from about 6 to about 20, from about 6 to about 18, or fromabout 6 to about 16.

Generally, olefin polymers of the present invention have low levels oflong chain branching, with typically less than 0.01 long chain branches(LCB's) per 1000 total carbon atoms. In some aspects, the number ofLCB's per 1000 total carbon atoms can be less than about 0.008, or lessthan about 0.005. Furthermore, olefin polymers of the present invention(e.g., ethylene polymers) can have less than about 0.004, less thanabout 0.003, less than about 0.002, or less than about 0.001 LCB's per1000 total carbon atoms, in other aspects of this invention.

Ethylene polymers can have a ratio of vinyl end groups to saturated endgroups that falls generally within a range from about 0.4 to about 0.9.In some aspects this ratio of vinyl to saturated end groups can be in arange from about 0.5 to about 0.9, from about 0.6 to about 0.9, or fromabout 0.65 to about 0.85.

Ethylene polymers disclosed herein can have less than about 0.002 longchain branches per 1000 total carbon atoms, and/or a ratio of Mw/Mn in arange from about 3 to about 20, and/or a ratio of vinyl end groups tosaturated end groups in a range from about 0.4 (or about 0.6) to about0.9, and/or a melt index less than 2.5, and/or a Mn in a range fromabout 15,000 to about 50,000, and/or a Mw in a range from about 100,000to about 300,000, and/or a Mz in a range from about 750,000 to about3,500,000. Further, certain polymers can have a Mw/Mn in a range fromabout 5 to about 15, and/or less than about 0.001 long chain branchesper 1000 total carbon atoms.

Polymers of ethylene, whether homopolymers, copolymers, terpolymers, andso forth, can be formed into various articles of manufacture. Articleswhich can comprise polymers of this invention include, but are notlimited to, an agricultural film, an automobile part, a bottle, a drum,a fiber or fabric, a food packaging film or container, a food servicearticle, a fuel tank, a geomembrane, a household container, a liner, amolded product, a medical device or material, a pipe, a sheet or tape, atoy, and the like. Various processes can be employed to form thesearticles. Non-limiting examples of these processes include injectionmolding, blow molding, rotational molding, film extrusion, sheetextrusion, profile extrusion, thermoforming, and the like. Additionally,additives and modifiers are often added to these polymers in order toprovide beneficial polymer processing or end-use product attributes.Such processes and materials are described in Modern PlasticsEncyclopedia, Mid-November 1995 Issue, Vol. 72, No. 12; and FilmExtrusion Manual—Process, Materials, Properties, TAPPI Press, 1992; thedisclosures of which are incorporated herein by reference in theirentirety.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a catalyst composition with an olefin monomerand optionally an olefin comonomer (one or more) under polymerizationconditions to produce an olefin polymer, wherein the catalystcomposition can comprise a metallocene compound having formula (I),(II), (III), and/or (IV), and an activator (e.g., an activator-support);and (ii) forming an article of manufacture comprising the olefinpolymer. The forming step can comprise blending, melt processing,extruding, molding, or thermoforming, and the like, includingcombinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

FIG. 1 presents the structures and corresponding abbreviations forhybrid metallocene compounds discussed in the examples that follow.Synthesis of the hybrid metallocene compounds was performed underpurified nitrogen atmosphere using standard Schlenk line or gloveboxtechniques. The solvent THF was distilled from potassium, whileanhydrous diethyl ether, methylene chloride, pentane, and toluene(Fisher Scientific Company) were stored over activated alumina. Allsolvents were degassed and stored under nitrogen. MET-A(η⁵-cyclopentadienyl titanium trichloride), MET-B(η⁵-pentamethylcyclopentadienyl titanium trichloride), and all of theorganic ligands were purchased from Aldrich Chemical Company. Productswere analyzed by ¹H NMR (300 MHz, C₆D₆, referenced against residual C₆D₆peak at 7.15 ppm).

Three general synthesis procedures were employed. In general procedure1, one equivalent of LiOR^(A) was added in one portion to a toluenesolution of CpTiCl₃ (or Cp*TiCl₃) in a glovebox at room temperature(about 22-25° C.). The reaction mixture was stirred at 50° C. overnight(about 12-16 hr). After the white solid (LiCl) was removed by centrifugeor by filtration, the solvent was removed under vacuum, resulting in ared or orange solid. The solid was recrystallized in a solvent mixtureof heptane and toluene to produce crystals of the respective hybridtitanium compound. In general procedure 2, a slight excess of NEt₃ inTHF (or diethyl ether) was added dropwise to a THF (or diethyl ether)solution of CpTiCl₃ (or Cp*TiCl₃) and one equivalent of HOR^(A). Theresulting suspension was stirred overnight at room temperature. Afterthe white solid (NEt₃.HCl) was removed by centrifuge or by filtration,the solvent was removed under vacuum, resulting in a red or orangesolid. The solid was recrystallized in a solvent mixture of heptane andtoluene to produce crystals of the respective hybrid titanium compound.In general procedure 3, one equivalent of HOR^(A) in toluene was addedto a toluene solution of CpTiCl₃, in a glovebox at room temperature. Thereaction mixture was stirred overnight at 90° C. The solvent was removedunder vacuum, resulting in an orange solid. The solid was recrystallizedin a solvent mixture of heptane and toluene to produce crystals of therespective hybrid titanium compounds. Analogous synthesis schemes tothese three general synthesis procedures can be employed to producehybrid zirconium or hybrid hafnium compounds (e.g., using CpZrCl₃ orCpHfCl₃).

MET-D, MET-E, and MET-F were produced in accordance with one of thesegeneral synthesis procedures. The synthesis procedures for MET-C, MET-H,MET-I, MET-J, and MET-K are described in more detail in the examplesthat follow. MET-G was prepared in a manner similar to that of MET-H,but triphenylsilanol was utilized instead of1,1,3-triphenyl-2-propyn-1-ol.

Polymerization experiments generally were performed as follows. Thepolymerizations were conducted for one hour in a one-gallon (3.785-L)stainless-steel autoclave reactor containing two liters of isobutane asdiluent, and hydrogen added from a 325-cc auxiliary vessel. Delta P ofhydrogen refers to the pressure drop in that auxiliary vessel from aninitial 600 psig (4.1 MPa) starting pressure. Hybrid metallocenesolutions (1 mg/mL) were prepared by dissolving 20 mg of the respectivemetallocene in 20 mL of toluene. Under isobutane purge, atriisobutylaluminum (TIBA) solution (25% in heptanes) was charged to acold reactor, followed by the hybrid metallocene solution and sulfatedalumina in toluene. The reactor was closed, and 2 L of isobutane wereadded. The reactor was heated to within about 5 degrees of the targetrun temperature, and the ethylene feed was opened. Ethylene was fed ondemand to maintain the target reactor pressure. The reactor wasmaintained at the desired run temperature throughout the run by anautomated heating-cooling system. Hydrogen was then introduced into thereactor during the polymerization process. For copolymerization,1-hexene was flushed in with the initial ethylene charge. At the end ofone hour, the isobutane and ethylene were vented from the reactor, thereactor was opened, and the polymer product was collected and dried.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238condition F at 190° C. with a 2,160 gram weight.

High load melt index (HLMI, g/10 min) was determined in accordance withASTM D1238 condition E at 190° C. with a 21,600 gram weight.

Polymer density was determined in grams per cubic centimeter (g/cc) on acompression molded sample, cooled at about 15° C. per hour, andconditioned for about 40 hours at room temperature in accordance withASTM D1505 and ASTM D1928, procedure C.

Molecular weights and molecular weight distributions were obtained usinga PL 220 SEC high temperature chromatography unit (Polymer Laboratories)with trichlorobenzene (TCB) as the solvent, with a flow rate of 1mL/minute at a temperature of 145° C. BHT(2,6-di-tert-butyl-4-methylphenol) at a concentration of 0.5 g/L wasused as a stabilizer in the TCB. An injection volume of 200 μL was usedwith a nominal polymer concentration of 1.5 mg/mL. Dissolution of thesample in stabilized TCB was carried out by heating at 150° C. for 5hours with occasional, gentle agitation. The columns used were threePLgel Mixed A LS columns (7.8×300 mm) and were calibrated with a broadlinear polyethylene standard (Phillips Marlex® BHB 5003) for which themolecular weight had been determined In the examples that follow, Mn isthe number-average molecular weight; Mw is the weight-average molecularweight; and Mz is the z-average molecular weight.

SEC-MALS combines the methods of size exclusion chromatography (SEC)with multi-angle light scattering (MALS) detection. A DAWN EOS 18-anglelight scattering photometer (Wyatt Technology, Santa Barbara, Calif.)was attached to a PL-210 SEC system (Polymer Labs, UK) or a Waters 150CV Plus system (Milford, Mass.) through a hot transfer line, thermallycontrolled at the same temperature as the SEC columns and itsdifferential refractive index (DRI) detector (145° C.). At a flow ratesetting of 0.7 mL/min, the mobile phase, 1,2,4-trichlorobenzene (TCB),was eluted through three, 7.5 mm×300 mm, 20 μm Mixed A-LS columns(Polymer Labs). Polyethylene (PE) solutions with concentrations of ˜1.2mg/mL, depending on samples, were prepared at 150° C. for 4 h beforebeing transferred to the SEC injection vials sitting in a carouselheated at 145° C. For polymers of higher molecular weight, longerheating times were necessary in order to obtain true homogeneoussolutions. In addition to acquiring a concentration chromatogram,seventeen light-scattering chromatograms at different angles were alsoacquired for each injection using Wyatt's Astra® software. At eachchromatographic slice, both the absolute molecular weight (M) and rootmean square (RMS) radius, also known as radius of gyration (Rg) wereobtained from a Debye plot's intercept and slope, respectively. Methodsfor this process are detailed in Wyatt, P. J., Anal. Chim. Acta, 272, 1(1993), which is incorporated herein by reference in its entirety.

The Zimm-Stockmayer approach was used to determine the amount of LCB.Since SEC-MALS measures M and Rg at each slice of a chromatogramsimultaneously, the branching indices, g_(M), as a function of M couldbe determined at each slice directly by determining the ratio of themean square Rg of branched molecules to that of linear ones, at the sameM, as shown in following equation (subscripts br and lin representbranched and linear polymers, respectively).

$g_{M} = {\frac{\left\langle R_{g} \right\rangle_{br}^{2}}{\left\langle R_{g} \right\rangle_{lin}^{2}}.}$

At a given g_(M), the weight-averaged number of LCB per molecule(B_(3w)) was computed using Zimm-Stockmayer's equation, shown in theequation below, where the branches were assumed to be trifunctional, orY-shaped.

$g_{M} = {\frac{6}{B_{3w}}{\left\{ {{\frac{1}{2}\left( \frac{2 + B_{3w}}{B_{3w}} \right)^{\frac{1}{2}}{\ln\left\lbrack \frac{\left( {2 + B_{3w}} \right)^{\frac{1}{2}} + \left( B_{3w} \right)^{\frac{1}{2}}}{\left( {2 + B_{3w}} \right)^{\frac{1}{2}} - \left( B_{3w} \right)^{\frac{1}{2}}} \right\rbrack}} - 1} \right\}.}}$LCB frequency (LCB_(Mi)), the number of LCB per 1000 C, of the i^(th)slice was then computed straightforwardly using the following equation(M_(i) is the MW of the i^(th) slice):LCB_(Mi)=1000*14*B _(3w) /M _(i).The LCB distribution (LCBD) across the molecular weight distribution(MWD) was thus established for a full polymer.

Example 1 Synthesis ofη⁵-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titaniumdichloride, MET-C

MET-C was prepared as follows. Approximately 50 mL of toluene (˜35° C.)was added to a flask with a mixture of 0.97 grams (4.42 mmol) ofη⁵-cyclopentadienyl titanium trichloride (MET-A) and 1 gram (4.42 mmol)of the lithium salt of 2,6-di-tert-butyl-4-methylphenol. The mixture wasstirred at room temperature for 1-3 days. After solid LiCl was removedby centrifuge, and toluene was removed under vacuum, the resultantproduct was recrystallized in a solvent mixture of toluene and heptane.Approximately 1.39 g of MET-C were produced; the yield was 75%.

Example 2 Synthesis ofη⁵-cyclopentadienyl(1,1,3-triphenyl-2-propynoxy)titanium dichloride,MET-H

MET-H was prepared as follows. Approximately 1.1 g (5 mmol) of ifcyclopentadienyl titanium trichloride (MET-A) was dissolved in 30 mL ofdiethyl ether, and the solution was cooled from −30 to −70° C. A mixtureof 1.42 grams (5 mmol) of 1,1,3-triphenyl-2-propyn-1-ol and 0.8 mL ofdry Et₃N in 30 mL of diethyl ether was added over 30 min. The reactionmixture was stirred as room temperature overnight. A white solid wasremoved by centrifuge. A light orange solid was obtained after diethylether was removed under vacuum. The resultant product was recrystallizedin toluene. Approximately 1.75 g of MET-H were produced; the yield was80%. FIG. 2 illustrates the ¹H-NMR analysis of the MET-H product.

Example 3 Synthesis ofη⁵-cyclopentadienyl(2,6-di-methoxyphenoxy)titanium dichloride, MET-I

MET-I was prepared as follows. Approximately 0.5 grams (2.28 mmol) ofη⁵-cyclopentadienyl titanium trichloride (MET-A) and 0.35 grams (2.28mmol) of 2,6-dimethoxyphenol were mixed in a cool toluene solvent (˜0°C.). After the reaction mixture was stirred at room temperature for 30minutes, the temperature was increased to 90° C. and stirred overnight.A dark red solid was obtained after toluene was removed under vacuum.The product was recrystallized in toluene. Approximately 0.67 g of MET-Iwere produced; the yield was 91%.

Example 4 Synthesis ofη⁵-cyclopentadienyl(6-allyl-2-methoxyphenoxy)titanium dichloride, MET-J

MET-J was prepared as follows. A 1.5-g (9.1 mmol)2-allyl-6-methoxyphenol solution in toluene was slowly added to asolution of 2 g (9.1 mmol) of η⁵-cyclopentadienyl titanium trichloride(MET-A) in toluene at room temperature. After the reaction mixture wasstirred at room temperature for 1 hr, the temperature was increased to90° C. and stirred overnight. An orange solid was obtained after toluenewas removed under vacuum. The product was recrystallized in toluene.Approximately 2.84 g of MET-J were produced; the yield was 90%. FIG. 3illustrates the ¹H-NMR analysis of the MET-J product.

Example 5 Synthesis ofη⁵-pentamethylcyclopentadienyl(2-allyl-6-methylphenoxy)titaniumdichloride, MET-K

MET-K was prepared as follows. A 1-g (6.9 mmol) 2-allyl-6-methylphenolsolution in toluene was slowly added to a solution of 2 g (6.9 mmol) ofη⁵-pentamethylcyclopentadienyl titanium trichloride (MET-B) in tolueneat room temperature. After the reaction mixture was stirred at roomtemperature for 1 hr, the temperature was increased to 90° C. andstirred overnight. A red solid was obtained after toluene was removedunder vacuum. The product was recrystallized in heptane. Approximately2.2 g of MET-K were produced; the yield was 80%. FIG. 4 illustrates the¹H-NMR analysis of the MET-K product.

Example 6 Preparation of Sulfated Alumina Activator-Supports

Sulfated alumina activator-supports were prepared as follows. Bohemitewas obtained from W.R. Grace Company under the designation “Alumina A”and having a surface area of about 300 m²/g and a pore volume of about1.3 mL/g This material was obtained as a powder having an averageparticle size of about 100 microns. This material was impregnated toincipient wetness with an aqueous solution of ammonium sulfate to equalabout 15% sulfate. This mixture was then placed in a flat pan andallowed to dry under vacuum at approximately 110° C. for about 16 hours.

Alumina A, from W.R. Grace Company, was impregnated to incipient wetnesswith an aqueous solution of 0.08 g ammonium sulfate per mL of water. Thealumina had a surface area of about 330 m²/g and a pore volume of about1.3 mL/gram. The amount of ammonium sulfate used was equal to 20% of thestarting alumina, by weight. The resulting mixture was dried in a vacuumoven overnight at 120° C., and then screened through a 35 mesh screen.To calcine the resultant powdered mixture, the material was fluidized ina stream of dry air at 550° C. for 6 hours. Afterward, the sulfatedalumina was collected and stored under dry nitrogen, and was usedwithout exposure to the atmosphere. This sulfated alumina was used asthe activator-support in Examples 7-61.

Examples 7-61 Polymerization Experiments Using Hybrid Metallocenes andSulfated Alumina

Table 1 summarizes certain polymerization reaction conditions andpolymer properties for Examples 7-61. Catalyst activities listed are inkilogram of polymer per mole of hybrid metallocene per hour (kgpolymer/mol Ti/hr).

A representative polymerization with MET-D and sulfated alumina wasconducted as follows. Approximately 2 mg of MET-D in 2 mL of toluenewere mixed with 300 mg of sulfated alumina in 2 mL of toluene in a glasstube under nitrogen. After about one min, this slurry was added to thereactor at below 40° C. The reactor was sealed and 2 L of isobutane wereadded and the contents were stirred at 700 rpm. As the reactortemperature approached 85° C., ethylene addition was begun, and the setpoint of 90° C. was rapidly attained. The reactor was held at 90° C. for60 min. The yield was 23,363 kg polymer/mol Ti/hr. See Example 10 inTable 1.

A representative polymerization with MET-E and sulfated alumina wasconducted as follows. Approximately 2 mg of MET-E in 2 mL of toluenewere mixed with 300 mg of sulfated alumina in 2 mL of toluene in a glasstube under nitrogen. After about one min, this slurry was added to thereactor at below 40° C. The reactor was sealed and 2 L of isobutane wereadded and the contents were stirred at 700 rpm. As the reactortemperature approached 85° C., ethylene addition was begun, and the setpoint of 90° C. was rapidly attained. The reactor was held at 90° C. for60 min. The yield was 27,776 kg polymer/mol Ti/hr. See Example 14 inTable 1.

A representative polymerization with MET-I and sulfated alumina wasconducted as follows. Approximately 2 mg of MET-I in 2 mL of toluenewere mixed with 300 mg of sulfated alumina in 2 mL of toluene in a glasstube under nitrogen. After about one min, this slurry was added to thereactor at below 40° C. The reactor was sealed and 2 L of isobutane wereadded and the contents were stirred at 700 rpm. As the reactortemperature approached 85° C., ethylene addition was begun, and the setpoint of 90° C. was rapidly attained. The reactor was held at 90° C. for60 min. The yield was 8,315 kg polymer/mol Ti/hr. See Example 26 inTable 1.

A representative polymerization with MET-J and sulfated alumina wasconducted as follows. Approximately 2 mg of MET-J in 2 mL of toluenewere mixed with 300 mg of sulfated alumina in 2 mL of toluene in a glasstube under nitrogen. After about one min, this slurry was added to thereactor at below 40° C. The reactor was sealed and 2 L of isobutane wereadded and the contents were stirred at 700 rpm. As the reactortemperature approached 85° C., ethylene addition was begun, and the setpoint of 90° C. was rapidly attained. The reactor was held at 90° C. for60 min. The yield was 22,994 kg polymer/mol Ti/hr. See Example 27 inTable 1.

A representative copolymerization with MET-J, sulfated alumina, andhydrogen was conducted as follows. Approximately 2 mg of MET-J in 2 mLof toluene were mixed with 300 mg of sulfated alumina in 2 mL of toluenein a glass tube under nitrogen. After about one min, this slurry wasadded to the reactor at below 40° C. The reactor was sealed and 2 L ofisobutane were added and the contents were stirred at 700 rpm. As thereactor temperature approached 85° C., 25 g of 1-hexene were added inwith ethylene and hydrogen (delta 45 psi or 0.31 MPa), and the set pointof 90° C. was rapidly attained. The reactor was held at 90° C. for 60min. The yield was 18,794 kg polymer/mol Ti/hour. See Example 52 inTable 1.

A representative polymerization with MET-K and sulfated alumina wasconducted as follows. Approximately 2 mg of MET-K in 2 mL of toluenewere mixed with 300 mg of sulfated alumina in 2 mL of toluene in a glasstube under nitrogen. After about one min, this slurry was added to thereactor at below 40° C. The reactor was sealed and 2 L of isobutane wereadded and the contents were stirred at 700 rpm. As the reactortemperature approached 85° C., ethylene addition was begun, and the setpoint of 90° C. was rapidly attained. The reactor was held at 90° C. for60 min. The yield was 27,623 kg polymer/mol Ti/hr. See Example 28 inTable 1.

Using 1H-NMR analysis, the ratio of vinyl end groups to saturated endgroups was determined for certain polymers produced, and abbreviated V/Sin Table 1. For these polymers, the ratio of vinyl end groups tosaturated end groups was in a range from 0.6 to 0.9.

FIG. 5 compares the molecular weight distribution of the polymer ofExample 14, produced using hybrid metallocene MET-E, and that of aconventional polymer produced using a standard metallocene catalystsystem. The molecular weight distribution is much broader for Example14.

FIG. 6 compares the molecular weight distributions of the polymers ofExamples 20 and 22, while FIG. 7 illustrates the molecular weightdistribution of the polymer of Example 47. Each of these polymers had arelatively broad molecular weight distribution.

FIG. 8 illustrates the radius of gyration versus the logarithm of themolecular weight for a linear standard and the polymers of Examples 34and 56, with data from SEC-MALS. FIG. 8 demonstrates these polymers weresubstantially linear polymers with minimal amounts of LCB's (long chainbranches).

TABLE 1 Polymerization Conditions and Polymer Properties for Examples7-61. Catalyst Sulfated 1- H₂ Catalyst Weight TIBA Alumina Hexene deltaPEthylene Temp Time Example Type (mg) (mL) (g) (g) (MPa) (MPa) (° C.)(min) 7 A 2 0.5 0.3 2.8 90 60 8 B 2 0.5 0.3 2.8 90 60 9 C 2 0.5 0.3 2.890 60 10 D 2 0.5 0.3 2.8 90 60 11 D 2 0.5 0.01 2.5 2.8 90 60 12 E 2 0.50.1 2.8 90 60 13 E 2 0.5 0.2 2.8 90 60 14 E 2 0.5 0.3 2.8 90 60 15 E 20.5 0.4 2.8 90 60 16 E 2 0.5 0.5 2.8 90 60 17 E 2 0 0.3 2.8 90 60 18 E 21 0.3 2.8 90 60 19 E 2 2 0.3 2.8 90 60 20 E 8 0.5 0.3 0.8 2.9 80 60 21 F2 0.5 0.3 2.8 90 60 22 G 2 0.5 0.3 2.8 90 60 23 G 2 0.5 0.3 0.22 2.8 9060 24 H 2 0.5 0.2 0.12 2.8 90 60 25 H 2 0.5 0.2 0.22 2.8 90 60 26 I 20.5 0.3 2.8 90 60 27 J 2 0.5 0.3 2.8 90 60 28 K 2 0.5 0.3 2.8 90 60 29 K2 0.5 0.3 2.4 80 60 30 K 2 0.5 0.3 3.4 105 60 31 K 2 0.5 0.2 0.12 2.8 9060 32 K 2 0.5 0.2 0.22 2.8 90 60 33 C 2 0.5 0.3 34 2.0 80 60 34 D 2 0.50.3 25 2.8 90 60 35 D 2 0.5 0.3 25 0.12 2.8 90 60 36 D 2 0.5 0.3 25 0.222.8 90 60 37 D 2 0.5 0.3 25 0.31 2.8 90 60 38 D 2 0.5 0.3 25 0.41 2.8 9060 39 D 2 0.5 0.3 25 0.50 2.9 90 60 40 D 2 0.5 0.3 57 0.46 2.8 90 60 41D 2 0.5 0.3 87 0.46 2.8 90 60 42 D 2 0.5 0.3 118 0.46 2.8 90 60 43 D 20.5 0.3 150 0.46 2.7 90 60 44 E 8 0.5 0.3 25 0.80 2.9 80 60 45 G 2 0.50.3 34 2.0 80 60 46 G 2 0.5 0.3 70 2.0 80 60 47 G 2 0.5 0.3 106 2.0 8060 48 H 2 0.5 0.2 57 2.8 90 60 49 H 2 0.5 0.2 118 2.8 90 60 50 J 2 0.50.3 25 2.8 90 60 51 J 2 0.5 0.3 25 0.12 2.8 90 60 52 J 2 0.5 0.3 25 0.312.8 90 60 53 J 2 0.5 0.3 25 0.50 2.9 90 60 54 J 2 0.5 0.3 25 0.92 2.9 9060 55 J 2 0.5 0.3 57 0.46 2.8 90 60 56 J 2 0.5 0.3 87 0.46 2.8 90 60 57J 2 0.5 0.3 118 0.46 2.8 90 60 58 J 2 0.5 0.3 150 0.46 2.7 90 60 59 K 20.5 0.3 57 2.4 80 60 60 K 2 0.5 0.3 118 2.4 80 60 61 K 2 0.5 0.3 150 2.480 60 Catalyst Catalyst MI HLMI Density Example Type Activity (g/10 min)(g/10 min) Mn/1000 Mw/1000 Mz/1000 Mw/Mn (g/cc) V/S 7 A 10474 0.032 8.98 B 13359 0.003 8.2 9 C 24524 10 D 23363 70.5 23.66 220.5 1690.1 9.32 11D 23793 0.025 3.9 43.40 235.7 843.7 5.43 12 E 12597 0.05 18.0 13 E 167520.095 26.4 14 E 27776 0.16 115.9 21.75 157.7 1399.8 7.25 15 E 193500.149 72.4 16 E 20211 0.12 34.9 17 E N/A 18 E 8541 0.336 75.1 19 E 142690.45 66.3 20 E 6269 0.025 13.6 32.74 245.8 2059.8 7.51 0.9631 21 F 277722 G 21448 0.195 572.8 21.52 197.5 2059.2 9.18 0.9669 23 G 12033 0.094298.3 24 H 1729 25 H 1145 26 I 8315 8.7 27 J 22994 0.02 15.3 25.59 216.01682.1 8.44 0.85 28 K 27623 0.024 9.1 22.42 290.6 3162.9 12.96 29 K11334 too low 1.6 30 K 18636 0.64 45.0 22.12 276.6 2610.8 12.5 31 K 922832 K 7121 33 C 6687 34 D 17960 0.47 39.6 24.62 171.9 1471.9 6.98 0.953635 D 12219 0.038 38.4 22.33 205.2 2084.5 9.19 0.9516 36 D 9425 0.474120.1 0.9502 37 D 10745 0.367 107.6 0.67 38 D 9210 0.39 79.9 39 D 98850.35 168.7 40 D 8811 1.04 151.6 17.21 185.0 2239.3 10.75 41 D 115132.465 129.7 16.11 158.8 2333.6 9.86 42 D 9041 2.1 185.2 43 D 9763 1.57138.9 44 E 7883 0.169 25.3 30.94 255.6 2438.4 8.26 0.9582 45 G 918622.07 182.8 2301.9 8.28 0.9583 46 G 14008 1.37 156.3 18.85 144.5 2008.77.67 0.9523 47 G 10747 2.06 224.9 17.72 131.5 2027.8 7.42 0.9501 48 H1075 49 H 2360 50 J 21640 0.69 38.9 21.07 165.9 1531.9 7.88 51 J 167470.597 49.2 52 J 18794 1.008 95.9 19.21 171.1 2051.8 8.91 53 J 16347 1.46126.2 54 J 9631 1.59 155.5 55 J 13276 1.47 123.3 56 J 9284 1.31 125.817.61 165.8 1929.9 9.41 0.9563 57 J 6994 0.92 104.6 0.9547 58 J 101005.29 250.9 0.9516 0.66 59 K 14965 0.09 10.1 60 K 17092 0.25 18.3 61 K12899 0.24 31.8

1. A compound having the formula:

wherein: M is Zr or Hf; X¹ and X² independently are a halide or asubstituted or unsubstituted aliphatic, aromatic, or cyclic group, or acombination thereof; and X³ is a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, wherein any substituentson X³ independently are a hydrogen atom or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof.
 2. The compound of claim 1, wherein M is Hf.
 3. The compound ofclaim 1, wherein M is Zr.
 4. The compound of claim 1, wherein X¹ and X²independently are a methyl group, a phenyl group, a benzyl group, or ahalide.
 5. The compound of claim 1, wherein X¹ and X² independently area halide.
 6. The compound of claim 1, wherein X³ is a substituted orunsubstituted cyclopentadienyl group.
 7. The compound of claim 1,wherein X³ is a substituted or unsubstituted indenyl group.
 8. Thecompound of claim 1, wherein any substituents on X³ independently are ahydrogen atom, a methyl group, an ethyl group, a propyl group, a n-butylgroup, a t-butyl group, or a hexyl group.
 9. The compound of claim 1,wherein: M is Zr; X¹ and X² are Cl; and X³ is a substituted orunsubstituted cyclopentadienyl group.
 10. The compound of claim 9,wherein any substituents on X³ independently are a hydrogen atom, amethyl group, an ethyl group, a propyl group, a n-butyl group, a t-butylgroup, or a hexyl group.
 11. A compound having the formula:

wherein: M is Zr, Hf, or Ti; X¹ and X² independently are a halide or asubstituted or unsubstituted aliphatic, aromatic, or cyclic group, or acombination thereof; and X³ is a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, wherein any substituentson X³ independently are a hydrogen atom or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof.
 12. The compound of claim 11, wherein M is Ti.
 13. The compoundof claim 11, wherein M is Zr.
 14. The compound of claim 11, wherein X¹and X² independently are a methyl group, a phenyl group, a benzyl group,or a halide.
 15. The compound of claim 11, wherein X¹ and X²independently are a halide.
 16. The compound of claim 11, wherein X³ isa substituted or unsubstituted cyclopentadienyl group.
 17. The compoundof claim 11, wherein X³ is a substituted or unsubstituted indenyl group.18. The compound of claim 11, wherein any substituents on X³independently are a hydrogen atom, a methyl group, an ethyl group, apropyl group, a n-butyl group, a t-butyl group, or a hexyl group. 19.The compound of claim 11, wherein: M is Ti; X¹ and X² independently area methyl group, a phenyl group, a benzyl group, or a halide; and X³ is asubstituted or unsubstituted cyclopentadienyl group.
 20. The compound ofclaim 11, wherein: M is Ti; X¹ and X² are Cl; and X³ is a substituted orunsubstituted cyclopentadienyl group.
 21. The compound of claim 20,wherein any substituents on X³ independently are a hydrogen atom, amethyl group, an ethyl group, a propyl group, a n-butyl group, a t-butylgroup, or a hexyl group.
 22. The compound of claim 11, wherein thecompound is: